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By Lars Rossemyr, Terkel Rosenqvist

The equilibrium Mn + 2 IiCl = MnCl2(g) + H2 has been studied at 1090°C for pure manganese and for Mn-Si alloys. For this reoction a standard free energy of Fo1363, = - 19,700 i 300 col ioas found. Combined with other thermal data, the standard free energy of the reaction Mn(s, ß) + Cl2 = MnCl2(g) was derived: Fo=- 56,140 + 9.78 T log T - 40.10 T For the formation of the various manganese silicides the following free energies were obtained. 5 Mn + 3 Si - M1z5Si3 ?F°1363 = -41,500 i 1500 cal Mn + Si - h.lnSi ?F°1363= -10,000 i 500 cnl Mn + 2 Si = MnSiz ?F°1363= -11,500 ± 500 cal In the search for a method suitable for the study of thermodynamic properties of certain alloy systems, it was found that the heterogeneous equilibrium between the alloy and a gas mixture consisting of hydrogen chloride, hydrogen, and volatile metal chlorides has considerable advantages. In addition to giving thermodynamic information about the alloys, such measurements may be used to derive thermodynamic data for the volatile metal chloride itself. The present paper gives some results which were obtained for manganese silicides and manganous chloride. Similar studies are presently being carried out for the iron silicides. The phase diagram of the Mn-Si system is rather well known,' but no information exists to the authors' knowledge about the thermodynamic properties of manganese silicides or about the chemical activities in molten Mn-Si alloys. At elevated temperature, manganese may react with hydrogen chloride according to the equation: Mn(s, ß ) + 2 HC1 = MnC1, (g ) + H2 [ 1] with the equilibrium constant The value of K, may be determined from measurements of the gas composition in equilibrium with pure manganese. When this value is used in connection with measurements on manganese alloys, the chemical activity of manganese in the alloy may be derived. Initial calculations showed that around 1000" to 1200°C the equilibrium constant K1 has a value of a few thousand, i.e., the reaction is shifted far to the right. In order to study this rather unbalanced gas composition, a flow method was used in two slightly different modifications. For all experiments with manganese silicides and for some experiments with pure manganese the apparatus shown on Fig. 1 was used. A bed of the metal or alloy was placed in a tube furnace. The refractory tube had an internal diameter of 14 mm and the bed was 75 mm long. Electrolytic manganese of high purity and silicon, 99.95 pct Si, were used as raw materials. All alloys were prepared by melting weighed amounts of the elements in a high frequency induction furnace in argon atmosphere. The melting was done in a silica crucible which was placed inside a graphite shell. The alloys were crushed to - 10 +40 mesh and analyzed chemically. Also, for the pure elements, the same size fraction was used. A controlled gas mixture of purified hydrogen and from 3 to 12 pct HC1 was passed through the bed where it reacted with manganese according to Eq. [I]. The volatile manganese chloride was collected in a condenser placed in the cooler part of the furnace tube. The gas mixture before and after the furnace was sampled and analyzed by absorption of

Jan 1, 1962

By S. C. Schaeker, A. W. Schlechten, A. H. Larson

PARRAVANO and Malquori' studied the equilibrium of H2S-Hz with molybdenum and its lowest sulfide which they believed to be MoS2. Mc Cabe' has shown that its composition is actually Mo2S3 and determined its dissociation pressure by means of Knud-sen effusion measurements. Stubbles and Richard- son3 have recently studied the equilibrium of gas mixtures of H2S-HZ with the two-phase solid mixtures of Mo-MozS3 and Mo2S3-MoS2. The latter investigators found that M02s3 deviated slightly from the stoichiometric composition, but they did not determine the homogeneous region of the disulfide phase. Morimoto and Kullerud, studied the Mo-S system by quenching, microscope, and X-ray methods and concluded that the disulfide is stoichiometric. The present investigation was concerned with the measurement of the sulfur vapor pressure variation with composition at 1100°C in the homogeneous region of "MoS2". These measurements were made by reacting: 1) molybdenum powder (99.97 pct Moj with sulfur vapor, and 2) MoS1.g9 (formed by reaction of Mo + H2S) with sulfur vapor in a quartz capsule. Conditions were controlled to form an equilibrated phase within the homogeneous region of the disulfide. The quartz capsule was sealed off initially under a vacuum and the residual gases were gettered by titanium powder contained in one end of the capsule. A mixture of Mo + S or MOS,., + S was in the other end. The section containing the titanium powder was heated for 24 hr at 700°C and then removed by flame sealing. The end of the capsule containing the charge was then heated to 1100°C. The other end of the capsule was maintained at a temperature which would produce the desired sulfur pressure in the capsule (liquid sulfur distilled from the charge mixture was retained in this end). After equilibration, the capsule was removed from the heating assembly and rapidly air-cooled. It is assumed that equality existed between the total sulfur pressures (PT) in the two ends of the capsule and not between the partial pressures of the different molecular species (S, SZ, Three separately controlled heating elements were used to maintain the proper temperature gradient over the length (approximately 12 in.) of the capsule. A thermocouple-Wheelco "Capacitrol" system was used for temperature control of the two end heating elements within 2"C. The center heating element was controlled directly by a " Power -stat". Separate controlling and measuring thermocouples were used for both end heating elements. Pt-Pt(l0 pct Rh) thermocouples were used for 1100°C and Chromel-Alumel thermocouples were used for lower-temperature control and measurement of the assembly. Silver foil was wrapped around the end of the capsule containing the liquid sulfur to insure a constant temperature zone. The thermal gradient over the entire length of the capsule was measured to: 1) ascertain that the length of the constant temperature zone of the liquid-sulfur end and the sulfide end was sufficient, and 2) ascertain that the liquid-sulfur zone was the zone of lowest temperature. The data obtained in this investigation are shown in Fig. 1 and Table I. The total sulfur pressure (PT) and p(S2) were calculated from the data of Braune et UZ.~ The compositions of the equilibrated disul-

Jan 1, 1964

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc.* When Mr. Carnegie made his gift which made possible a home for the engineering societies, a separate corporation was organized to act as a holding company and to manage the common property. This was long known as the United Engineering Society but the name has now been changed to one which more nearly reflects the real function of the corporation. It holds title to the Engineering societies Building and to various funds placed in its charge and is managed by a Board of Trustees of which three are chosen by each of the four societies, American Institute of Mining and Metallurgical Engineers, American Society of Mechanical Engineers, American Institute of Electrical Engineers and American Society of Civil Engineers, which own equal and undivided interests in the property. The land and building cost two million dollars. The interest of each of the Founders societies, aside from especial trust funds, is now valued at $493,352. The A. I. M. E. trustees are Arthur S. Dwight, J. V. N. Dorr and H. A. Guess. George D. Barron will succeed Mr. Guess as trustee at the end of this year. The President of the Board is Francis Lee Stuart and the Secretary, Alfred D. Flinn. The Engineering Foundation The Engnieering Foundation was established in 1814 as a result of a gift of $200,000 made by Ambrose Swasey. It is intended not only "for the Furtherance of research" along broad lines but also "for the advancement of" a wide variety of other activities of benefit to engineering as need arises. The endowment fund, which now amounts to $630,000, is administered by the United Engineering Trustees, Inc. Through The Engineering Foundation board, on which the Institute is now represented by J. V. N. Dorr, John M. Callow and Galen H. Clevenger, the income of the endowment, approximately $28,000 a year, and funds contributed for special projects are appropriated for the purposes intended. H. C. Bellinger will succeed Mr. Callow on the board at the end of this year. Alfred D. Flinn is Secretary- and Director. Researches of wide interest in many lines have been aided by Engineering Foundation. . A grant from it to the Mining Methods Committee assisted in the preparation of Volume 72 of the Transactions. For several years the Foundation has aided in support of the study of Blast-furnacc Slags by R. 8. McCaffery at the University of Wisconsin, sponsored by the Institute. The Foundation has raised over $230,000 to support the Alloys of Iron Research endorsed by the Institute and George B. Water-house is serving as Chairman and Director of the Iron Alloys Committee which has been brought together to direct this work. The Foundation has also on recommendation of the Institute made a grant in aid of the studies of Mining and Strata being conducted at Columbia University by P. B. Bucky, which promise information of great usefulness relative to mine subsidence and support of ground. John Fritz Medal Board of Award The medal was established in 1902 and lias since, been awarded not oftener than annually by a hoard of sixteen members, four representatives each from the American Societies of Civil, Mining and Metallurgical, Mechanical, and Electrical Engineers.

Jan 1, 1930

By Lyon F. Terry

IN contemplating the prospects of natural gas being transported from the fields where it is produced to such distant points as Philadelphia, New Jersey, New York City, and New England, let us review the advance that natural gas has made and the projects currently scheduled for construction. This may give us a perspective of the point in the long-range development of the natural gas business in which we now find ourselves, and some basis for judging the further expansion of the industry. Authentic statistics of the total marketed production of natural gas in the United States have been compiled by the Bureau of Mines since the year 1906. The growth of the business is indicated by the following data on marketed production for each ten-year interval since 1906:

Jan 1, 1947

[A session of the Institute of Metals held during the February, 1926, meeting of the Institute, was devoted to a symposium on ''gas" in copper. S. Skowronski, Perth Amboy, N. J., was chairman. On the program were papers by T. S. Fuller; W. H. Bassett and J. C. Bradley; Susan B. Leiter, and W. H. Bassett and H. A. Redworth. These papers follow the chairman's introductory discussion.] S. Skowronski, Perth Amboy, N. J.—There are today two groups of metallurgists, one group who believe in oxygen-free copper and another group who believe that oxygen is absolutely essential in copper; not that the two groups disagree, but that a certain grade of work calls for oxygen-free copper, while another grade of work does not. I can sum up the problem by reading the abstract of an article by Frederick Johnson of Great Britain in The Metal Industry of Sept. 4, 1925. Few, who have watched the trend of things during the last two decades, can have failed to notice the steady growth of opposition to the prevalent use of copper in the "tough-pitch" condition, which for many ages enjoyed an unchallenged supremacy. Broadly speaking, there are two schools of thought in the metallurgical world, one holding the view that copper containing a small proportion of oxygen is an eminently suitable material for users, the other expressing its preference, in no hesitating or uncertain manner, for copper from which oxygen has been removed by means of a deoxidizer. In the old days, before the advent of the converter and the electrolytic refining process, the copper of commerce was so impure that the presence of oxygen was imperative in order to neutralize the influence of impurities which militated against the hot-working properties of the metal. For electrical purposes, oxygen must be present, because sound bars and billets cannot be produced without it, except at the expense of electrical conductivity. For most engineering purposes, however, electro-deposited copper may be used either by itself or with the addition of alloying elements, e. g., arsenic and nickel, which experience has proved to be beneficial, such copper being freed from oxygen by the aid of a deoxidizer, e. g., phosphorus. Such material has positive advantages over "tough-pitch" copper as at present produced from refinery furnaces. It has greater toughness and malleability, and is immune from the action of reducing gases at high temperatures, the destructive action of which, in the case of "tough-pitch" copper, is well known. The reasons why there has been no wholesale replacement of "tough-pitch" copper by deoxidized copper are commercial in nature; copper can be more economically melted in large-capacity furnaces which lend themselves to the poling process and are not so suitable for control of uniformity of action of deoxidizers as the smaller electric or crucible furnaces, whilst they are also more convenient for the production of very large castings. Moreover, the equipment of most large copper manufacturing plants is designed for casting "tough-pitch " copper in open moulds, e. g., wire bars and cakes, and these could not be used for deoxidized copper, which must be cast in vertical moulds as in brass-shop practice. Further, there are still certain impure brands and

Jan 1, 1926

By J. H. Polhems, R. B. Brackin, D. B. Grove

THE heavy media separation process plays an outstanding role in the concentration of 4000 tons of zinc ore per day at the Mascot mill of the American Zinc Co. of Tennessee. Of the total tonnage, 72 pct is treated in the heavy media separation plant to reject 56 pct of the ore as a coarse tailing, which has a ready market. Concentrates from this separation are beneficiated further by jigging and flotation. Approximately 25 pct of the total zinc concentrate production is made in the jig mill. Jig tailings are ground and pumped to the flotation circuit where the balance of the production is made. Fig. 1 shows a generalized flowsheet of the mill. The Mascot ore is a lead-free, honey-colored sphalerite in dolomitic limestone, with lesser amounts of chert and some pyrite. A mineralogical analysis is given in Table I. After 10 years of successful operation with galena medium and treatment of nearly 10,000,000 tons of ore, a decision to convert to ferrosilicon was made early in 1948 because of the increasing price of galena and consequent high operating costs. The conversion was made on Nov. 6, 1948, and the results obtained since that time have shown remarkable improvement over those made with galena. The Table I. Mineralogical Analysis of Mill Feed, Pct Calcium carbonate 49.5 Magnesium carbonate 35.2 Iron oxide and aluminum oxide 1.5 Zinc sulphide 4.5 Insoluble 9.3 100.0 Table II. Comparative Data, Galena and Ferrosilicon Ferro- Diner-Gelenaa siliconb ence Operating costs per ton milled, ct. 21.21 9.12 12.09 Medium consumption per ton milled, lb 0.80c 0.15 0.65 Reagent consumption per ton milled, lb 0.45 0.02 0.43 Tailing assay, pct Zn 0.310 0.297 0.013 Concentrate. oct Zn 12.08 10.33 1.75 Heavy medla ieparatlon recovery. pct 89.38 90.22 0.84 Mill feed rate, tons per hr 153 166 13 Heavy mesa separation feed rate. tons per hr 100 10 0 Tons milled per heavy media separation man shift 350 620 270 Mill feed to coarse tailings, pct 51.0 56.7 5.7 Lost mill time, pct 5.6 5.0 0.6 Power consumption, kw-hr per ton 2.06 1.92 0.14 a 1947. " First 6 months of 1950. c Net consumption after deducting credit for reclaimed waste galena. Consumption of new galena was 1.320 lb per ton milled. For entire life of galena operation, a credit of 40 pct of the value of the new galena added was realized from the sale of waste galena. comparisons given in this report cover the first 6 months of 1950 as representing the ferrosilicon operation, and the year 1947 as representing the galena operation. This was the last full year in which galena was used exclusively and is representative of the best work done during the 10 years of operation with this medium. After only 2 years' operating experience, with ferrosilicon and treatment of 1,807,585 tons many advantages have been revealed and are summarized in Table 11. Development Prior to the introduction of the heavy media process, all the mill feed was crushed through 5/8 in. and treated by jigging. A finished tailing assaying 0.66 pct Zn was made on rougher bull jigs, and cleaner jig tailings were ground for treatment by flotation. The first test work on the sink-and-float method of mineral beneficiation was carried out at Mascot in 1935, using a 3-ft cone and galena medium for batch tests. The following year a 6-ft cone was installed for pilot-plant work. This unit became a part of the mill circuit on March 1, 1936, and handled a gradually increasing tonnage in the next 2 years as the process developed to the point where it could treat all the + 3/8-in. material in the mill feed. Coarse jigging was then discontinued on March 1, 1939, and all coarse tailings have been made by the heavy media separation plant since that time. Feed Preparation: The original feed preparation plant consisted of a drag washer followed by two 4x10-ft Allis-Chalmers washing screens. A surge bin and two additional 5x12-ft AC washing screens were added in 1943. Use of primary and secondary washing screens was found essential to provide the cleanest possible feed for the cone and thereby avoid excessive contamination of the galena medium. Improved washing was obtained by replacing the drag washer with a 7x20-ft Allis-Chalmers scrubber, shown in Fig. 2, which has been in service since May 1944. Throughout the life of the galena operation, delivery of extremely muddy ore to the mill overloaded the medium cleaning system, and it frequently was necessary to cut off the feed and clean the medium for several hours until its normal viscosity had been re-established. The cleaning circuit

Jan 1, 1952

By Harvey S. Mudd

WHEN talking about Europe it is well to endeavor to keep politics and economics apart but they have become so intermingled in recent years that the discussion of one topic inevitably leads to the other. Economic influences formerly prevailed over politics but today national and international economies are governed by political forces. Commerce in raw materials, food, and manufactured products is now so restricted by governmental controls that the capacity of the world to produce and to consume, to exchange goods and to pay for them, cannot be gauged by the past or predicted by a multitude of experts. In prewar days there were some yardsticks but today there are none. Thus it is hazardous to make forecasts, for in all fields of human effort the world has been cast upon an uncharted sea.

Jan 1, 1947

By John M. Lovejoy

CURRENT production of petroleum on such a vast scale presents many interesting problems- the solutions of which are important not only to those directly interested in the business, but to the nation as a whole. The industry is relatively young. Until the discovers of the Lucas gusher at Spindletop in 1901 petroleum production had not exceeded 60,000,000 bbl. per year compared with 1,100,000,000 bbl. in 1936. In 36 years then, the modern oil business, production, transportation, refining, and marketing has developed. I will first present a brief history. of oil production as a background for consideration of the present situation.

Jan 1, 1937

By James Douglas

THOUGH liberality is not supposed to be a prominent trait of the Scottish character, Canada owes to a Scotchman, Sir Wm. Macdonald, more than to any other of its people, not only wise ideas, but pecuniary help towards extending education: and another Scotchman, in New York, has sumptuously housed under one roof three branches of the engineering fraternity, of which we are one. Having thus created us members of the same family-for the metaphorical meaning of house and kinship is identical-Mr. Carnegie expresses more emphatically than even he could in words, that, by affording facilities for closest intercourse, he in¬vites the mechanical, electrical and mining engineers to par¬ticipate in the freest interchange of idea and experience, and to correlate and combine the results of their studies and activi¬ties; and, being members of the same household, to banish re¬serve and secrecy. And now we, the members of the - American Institute of Mining Engineers, meet as though we were at home in a neighboring country. For whether we meet in Canada, in England, or elsewhere, the Institute is always received as though no political or geographical divisions separated its members from those of congenial associations in the land of its host. In truth, the title which we have assumed claims for the sphere of our activities the whole American continent, regardless of such trifling details as boundary-lines. The fact that we meet to communicate each other's experience, to discuss our difficulties, and to seek each other's aid in solving the intricate problems that so often present themselves in the course of our profes¬sional life, is an acknowledgment of our individual helpless¬ness; and therefore an argument for united effort. But no effort can be of any value if there is an underlying suspicion

Jan 9, 1907

By Gill Montgomery

At this moment in the history of the world, the all- pervading and universally most important fact is that the world population is beginning to outgrow its food supply, and the United States has suddenly lost its ability to give away huge food surplus to any nation in the world with a food shortage problem. This, of course, means that, all of a sudden, our government must completely reverse its former bureaucratic stance regarding crop controls and agricultural price supports, to out-right incentives to increase farm production and bring more idle land into food-growing use.

Jan 2, 1967

By Olin M. Hart

Uranium ores occur in the Lower Cretaceous Inyan Kara group of heterogeneously stratified fluvial and fluvial-marine sandstones in the Black Hills of western South Dakota and northeastern Wyoming. There are three principal mining districts, each in the ancestral and present drainage area of a major river partially responsible for stripping the region to its present topographic form. Primary minerals in the deposits are coffinite and uraninite with minor amounts of paramontroseite and haggite. The ore minerals coat sand grains and fill interstices of complexly cross-stratified sandstone along solution fronts similar to "roll" type deposits of the other districts. Minerals of oxidized deposits are typically carnotite and tyuyamunite with different proportions of secondary vanadium accessory minerals. Ground water was the transporting medium and deposition of primary uranium and vanadium minerals occurred in reducing environments produced and controlled by physio-chemical characteristics of the sedimentary rocks.

Jan 1, 1968

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By J. F. Breedis

The morphology and crystallography of marten -site formed during quenclzing were examined by transmission electron microscopy in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pet Ni and Fe-33 wt pet Ni. Depending upon composition, four types of transformation products were observed in this portion of the Fe-Cr-Ni system. Three of these products are denoted as lath, plate, and surface martensite. The hcp structure found in association with martensite it? certain higlz-clzromium stairzless steels does not influence the transformation crystallogyaphy and cannot he Considered to act as a transitional structure in the transformation from austenite to martensite. DISTINCT changes in the characteristics of mar-tensitic transformations are produced by the partial replacement of nickel by chromium in austenitic iron alloys. Large, discrete martensite plates form in Fe-30 pct Ni, while aggregates of small crystals form in sheets parallel with (111)A austenite planes in stainless steels containing in the vicinity of 18 pct Cr and 8 pct Ni. These transformation structures are termed plate and lath martensite, respectively. In addition, an hcp structure (E) has been observed in certain high-chromium stainless steels in association with martensite. It has been suggested that the E structure acts as an intermediate step in the nucleation of martensitel-' and influences the morphology and crystallography of the final transformation product. However, this structure may be the consequence of the deformation of austenite arising from the shape distortion accompanying the transformation to bcc martensite.' An hcp stacking of atoms is produced in an fcc lattice by the introduction of an intrinsic stacking fault on alternate (111)A planes. At present, the arguments behind each explanation for the E structure are based on circumstantial evidence. This investigation seeks to determine the importance of the hcp structure to the martensitic transformation, and to examine the crystallography and morphology of the structures produced in bulk samples by quenching in alloys whose compositions lie between Fe-19 wt pct Cr-11 wt pct Ni and Fe-33 wt pct Ni. These aspects of the martensitic transformations occurring in these alloys have been studied by electron metallography and selected-area diffraction of foils examined in transmission in the electron microscope. EXPERIMENTAL METHODS The alloys have been prepared from thoroughly mixed powders of pure iron (99.6+ pct, 0.06 max pct C, 0.15 max pct N), chromium (99.9+ pct), and nickel (99.9+ pct). After sintering in an Ar-H2 atmosphere, the mixtures were melted by induction heating in recrystallized alumina boats under purified argon. The ingots were cold-rolled to 0.4-mm sheets (100 pct reduction in thickness) after the removal of at least 1.5 mm from their surfaces by grinding. Three-millimeter discs were punched from the cold-rolled sheet and annealed at 1150°C for approximately 24 hr in evacuated quartz capsules. The average grain size was 40 µ Thin foils for examination in transmission in the electron microscope were prepared from discs quenched to liquid-nitrogen temperature. A depression was first jet-machined into the center of a disc and a thin area (less than approximately 3000A in thickness) was produced at the base of the depression by electropolishing. Electron-microscope studies utilized the RCA EMU-3 and the Philips EM-100B microscopes operating at 100 kv. X-ray examination of the polycrystalline alloys was performed either in a diffractometer or in a

Jan 1, 1964

By W. M. Lehrer

RECENT development of high-temperature brazing alloys has required information regarding the eutec-tic temperature and composition of the Pd-rich section of the Pd-B system.. Literature on this subject was found to be scanty with no complete system yet determined. Buddery and welch1 report an inter-metallic compound occurring in the Pd-B system at 6.33 wt pct B (PdsBz). Another source, Sieverts and Bruning,2 indicates that after annealing at 700°C, a 1.6 and a 2.0 wt pct B alloy were two phase whereas a 0.75 pct B alloy was single phase. Recent work3 using a hot-stage microscope has proposed a eutectic temperature of 743OC. This method utilized the observation of the onset of incipient melting at grain boundaries. The eutectic composition, however, was not determined. METHODS AND PR0CEDURES Five alloys were prepared by triple inert arc-melting high-purity palladium (95.98 pct) with additions of 2 to 6 pct purified amorphous boron. The alloys were crushed within a hardened steel mortar with a steel pestle. The 2 pct alloy, however, was too tough to be crushed in the above manner so was crushed by successive reductions through a rolling mill. Approximately 17 to 18 g of the crushed alloy was used in the thermal analysis. The alloys were melted in pure quartz crucibles. The thermocouple protection tubes were also of quartz and fused along the inside wall of crucibles to prevent floating of the thermocouple. This was an expediency as centering of the thermocouple in the melt would have been preferable. Melting was done in a tube furnace with a slow flow of tank helium maintained as a protective atmosphere. Heating and cooling rates were maintained at 3.5OC per min through the critical temperature ranges by means of a synchronous motor hook-up to a furnace controller. All specimens were heated to 100°C over the indicated liquidus on heating prior to reversing to the cooling cycle. Specimens emerged from the furnace with mirrorlike brightness attesting to the protective quality of the helium atmosphere. Thermal arrests were detected by the differential thermocouple technique using chrome l-alumel couples and nickel as the reference specimen. Arrests were recorded on a Leeds-Northrup automatic X-Y recorder. The specimen temperature and temperature difference were read to + 7.5OC and ± 1.5OC, respectively. These readings were well within the sensitivity of the instrument amplifier. Chromel-alumel couples were used in lieu of Pt-Rh as very few arrests were contemplated in excess of 1200" to 1300°C, the approach of instability. No standardization was performed on these thermocouples subsequent to their use. RESULTS The thermal arrest temperatures obtained are plotted in Fig. 1 as a function of wt pct B. The composition function was obtained by chemical analysis of portions of the specimens after the thermal analysis was completed. The 2 to 6 pct nominal alloys were found to have 1.80, 2.35, 3.65, 4.18 and 5.90

Jan 1, 1960

By N. J. Grant, H. Brunner

This paber is concerned with the determination of equations relating elongation to the amount of shear taking place both along grain boundaries and in slip planes of poly crystalline aggregates during creep. Certain discrepancies with previously used equations are pointed out. Grain boundaries were observed to become serrated during creep, but it is shown that this does not necessarily prevent further grain boundary sliding. Direct obser-vations of subgrain boundary ingration lead to the conclusion that this migration facilitates sliding along serrated grain boundaries. It is bointed out that the state of stress at triple boints is still unknown. MOST of the mechanisms of deformation contributing to elongation are shear processes, such as slip, kinking, grain boundary sliding, and twinning. For quantitative investigations of individual deformation mechanism it is necessary to know the equation which permits the calculation of speci-tnen elongation from measured amounts of shear. This calculated elongation must then be compared with the observed total elongation. The authors' special interest concerned grain boundary sliding during creep. Although this subject has already been investigated quantitatively by McLean,' Rachinger,' and Fazan, Sherby, and Dorn, calculations indicated that none of the equations used thus far to relate shear with elongation were sufficiently well founded. A basic study of this relationship was thus made and the results of this study (which do not entirely agree with those previously used) are presented. Most of the ideas set forth apply not only to grain boundary sliding but to other mechanisms of shear as well. THE SPEAR-ELONGATION RELATIONSHIP Basic Models—The relationship between shear and elongation is trivial in the simplest case of shear, which is shown in Fig. l(a). The vector A; designates the displacement across the shear interface, and Au, and Aut are its components parallel and normal to the tensile direction, respectively. It is evident that the specimen elongation due to shear is equal to the longitudinal component of the shear vector, and it should be noted that the normal component does not contribute to the elongation of the specimen (there are, of course, two normal components in a three-dimensional model). The model shown in Fig. l(b) may be applied to mechanical twinning and to subgrain boundary tnigration. In this case the width (h) of an already existing shear band increases by the migration of an interface, but the shear angle y (angle of mis-orientation in the case of a subgrain boundary) remains constant. The geometrical relationships indicated in Fig. l(b) permit this case to be reduced to the one shown in Fig. l(a). For the resulting elongation A6 we find: where AV/V = fraction of the volume of the specimen swept by migrating interfaces , and 1 = length of specimen. Thus, assuming for example that the angle of mis-orientation is 1 deg, and that P = 45 deg, we find that the specimen elongates 0.87 pct of its length if the entire volume of the specimen is swept once by such a subgrain boundary. An example of deformation by migration of subgrain boundaries is shown in Fig. 2. The specimen shown was repolished after 9.8 pct creep strain and the test then continued for another \ pct. Since the shear vector has, in general, a component normal to the surface, subgrain boundary migration results in the formation of an inclined band delineating the region swept by the subgrain boundary. These inclined bands become clearly visible when observed with oblique illumina-

Jan 1, 1960

By M. Kaufman, A. E. Palty

The phase structure and aging characteristics of two nickel-base alloys, Inconel 718 and 702, were investigated. Wrought and cast Inconel 718 showed ArisCb as the major hardening phase, as well as ture was positively identified. Inconel 702 had Ni3Al as the major hardening phase, as well as Cr7C3-of the phase amounts with temperature was determined. 1 HE value of phase structure and aging rate information in the utilization of alloys has been well established. As part of a continuing program, the results obtained on two nickel-base alloys, hconel 718 and Inconel 702, are presented here. Inconel 718 is a relatively new alloy considered for application in both sheet and cast form. Its novelty lies in the use of high columbium tantalum levels in a Ni-Cr-Fe base. No previous work on this type of alloy has been reported in the literature. Inconel 702 is being used now as an oxidation-resistant sheet alloy. Occasional fabrication problems spurred work on its basic structural behavior. The composition of 702 is essentially nichrome plus aluminum and titanium for strengthening and added oxidation resistance. This puts it in the basic class of other nickel-base alloys which have already been studied. The two alloys will be treated separately. INCONEL 718 Phase Study Methods. The phases present after the various conditions investigated were determined by X-ray diffraction analysis of two different elec-trolytically extracted residues and microscopic examination. The extraction methods, using 10 pct HC1 in alcohol and 10 pct H3PO, in water and the X-ray technique have been described previously.' The effect of temperature on the phase behavior was studied on sheet material using the following heat treatments: 2250°F, 2 hr, ice brine quench 1300 100 hr, water quench 2250°F, 2 hr, ice brine quench 1400°, 100 hr, water quench 2250°F, 2 hr, ice brine quench 1500°F, 100 hr, water quench 2250o 2 hr, ice brine quench 1700°F, 48 hr, water quench 2250°F, 2 hr, ice brine quench 1850°, 24 hr, water quench 2250°, 2 hr, ice brine quench 2000°F, 6 hr, water quench The high solution temperature was an attempt to dissolve as many phases as possible without causing melting. Aging exposures were made longer than normal heat treating times in order to approach equilibrium conditions more closely. Cast material was examined only in the as-cast condition and with the normal heat treatment (1700°F, 1 hr, air cool 1325oF, 16 hr,air cool). Materials. The full phase study was performed on sheet specimens approximately 1/2 in. by 2 in. by 1/16 in. The cast pieces were cut from the gating system of a vacuum-cast test piece. An all weld-metal specimen was made by running many weld beads on the sheet using filler made from the sheared edges of the sheet. All external contamination was removed by belt-sanding followed by an electro-polishing treatment. The typical composition of wrought Inco 718 is as follows: The alloy is air-melted. Cast hco 718 may have higher molybdenum. Due to the expectation of finding a Ni-Cb phase (Ni, Cb) for which no X-ray diffraction pattern was available in the ASTM Index, a special 5 Ib heat to the stoichiometric composition of this intermetallic

Jan 1, 1962

By J. C. Scully, G. Sanderson

The electrolytic formation of y hydride in thin foils of Ti-5Al-Z.5Sn alloy and four Ti-A1 binary alloys has been studied by electron microscopy and electron diffraction. Two orientation relationships have been found: THE adsorption of hydrogen by titanium alloys from aqueous solutions has been widely reported. This can occur, for example, in both alkaline' and acidic2 pickling baths, in chemical polishing374 and electro-polishing Solutions,3,4 during cathodic polarization5" and under certain corrosion conditions,7,8 Etching reagents may also produce visible precipitates, sometimes after an aging period.9 During an investigation into the stress corrosion susceptibility of a titanium alloys by thin foil electron microscopy many observations have been made of hydride precipitation which has been deliberately promoted by techniques that are described below. The characteristics of hydride precipitation are reported and the observed crystallographic orientation relationships are discussed with reference to distortion in the titanium lattice created by the presence of the hydride. EXPERIMENTAL TECHNIQUE One grade of commercial titanium and five alloys were examined. Their composition and hardness values are shown in Table I. All the materials were in the form of thin sheet, 0.05 to 0.065 cm thick, which had been annealed after cold rolling. Foils suitable for transmission electron microscopy were made in two ways: a) by chemical polishing; and b) by elec-tropolishing. The solution used for chemical polishing was a mixture of 44 pct HF and 73 pct HNO3 in the volumetric ratio 2:3. During this polishing specimens were manually moved up and down in the solution. The reaction was veFy rapid, specimens thinning to foil thickness (2000A) in 5 min. Since chemical polishing solutions tend not to cause hydride contamination if they are kept cool3 no attempt was made to prevent the solution from becoming hot during the thinning operation. Electropolishing was performed at -30° C with a mixture3 composed of 295 cu cm methyl alcohol, 175 cu cm n-butyl alcohol, and 30 cu cm perchloric acid with an applied voltage of 40 v after chemically thinning specimens to approximately 0.017 cm thickness in a cool solution of 44 pct HF, 40 vol H2O2, and water in the volumetric ratio 1:6:3. EXPERIMENTAL RESULTS 1) Ti-5A1-2.5Sn Alloy. The Ti-5A1-2.5Sn alloy was severely contaminated by hydrogen during the chemical polishing. Foils obtained in this way contained large amounts of the y hydride phase. A typical micrograph is shown in Fig. l. The laths were identified as the hydride phase by selected-area diffraction of a large number of foils examined in a tilting stage that could be turned through 40 deg. Using the lattice spac-ings of the alloy obtained by X-ray diffraction as a standard the a value of the hydride was determined fromo the electron diffraction patterns to be 4.38 to 4.40A. The accuracy of this figure is only about ±2 pct. Further evidence of the identification was obtained by vacuum annealing chemically polished foils of the alloy at 500°C. This resulted in the dissociation of the hydride with the production of dislocations and possibly vacancy loops as shown in Fig. 2. The hydride

Jan 1, 1968

By J. Lemish

Considerable research has been conducted in Iowa in recent years on carbonate aggregate reactions in concrete. Groups outside the state have become active in the past few years after recognizing that certain carbonate aggregates are reactive in concrete. The paper reviews the nature and extent of the problem and a summary is given of research by the author and his associates. In recent years considerable research has been conducted in Iowa on carbonate aggregate reactions in concrete. The research is part of a general study on the behavior of carbonate rocks as concrete aggregates sponsored by the Iowa State Highway Commission. Research on carbonate aggregates has not been extensive in the past. Laughlin1 published one of the first papers on carbonate aggregates in 1928 and was followed by others, notably H. S. sweet,' B. Mather et al.,3 and K. Mather4 who emphasized the petrographic and physical aspects of carbonate aggregates. The recognition that certain carbonate aggregates are reactive in concrete has led to increased participation in research in the past few years by groups outside of Iowa. Significant contributions have been made by Swenson and Gillot,5 Hadley,6 and Chaiken and Halstead7 in work which emphasizes the expansion of carbonate rocks in alkaline environments and the reaction of carbonate minerals or dedolomitization with alkalies. It is the purpose of this paper to review briefly the nature and extent of the problem and present a summary of the research by the author and his associates. EXTENT AND NATURE OF THE PROBLEM The problem is the deleterious behavior of certain carbonate aggregates in concrete. It was first recognized in Iowa over 20 years ago when poor service records of certain highways were correlated with aggregates produced from the Glory and LeGrand quarries. Deleterious behavior of carbonate aggregates have been reported in Canada and, more recently, in New York and Virginia. As more knowledge is gained concerning the problem, distress in concrete related to carbonate aggregates may be recognized over a widespread area. The problem may potentially exist in the Midwest, the Northeast, and other parts of the country underlain by thick sections of carbonate rocks readily available for utilization as aggregates. The nature of distress in Iowa highways is a general weakening and deterioration of concrete characterized by progressive cracking and spalling away from joints and edges (Fig. 1). The distress generally occurs after 15 years of service and becomes progressively worse. Specimens of such concrete lack the toughness of sound concrete and break easily under the hammer in the manner of a soft brick. The matrix is generally highly carbonated and dark borders, or reaction shells or rims outline the argillaceous carbonate aggregate fragments (Fig. 2). Cracks observed in cores cut across the aggregates and concrete matrix. Although localized volume change (expansion) is associated with spalling, there is no definite field evidence in Iowa that excessive growth of concrete slabs has occurred. The experience with carbonate aggregates in Iowa indicates that the concrete deterioration is not the same as that induced by the alkali-aggregate reaction associated with siliceous aggregates. The principal difference is that in Iowa the distressed concrete is weakened throughout the slab. In concrete affected by the alkali aggregate reaction, the

Jan 1, 1961

By A. Heim, M. Gondouin

Invasion experiments were run on Berea sandstone cores to get laboratory measurements of resistivity and saturation profiles characteristic of water and oil sands invaded by mud filtrate. Injection rates were as low as 1.13 cm/D, and the cores were 30 to 36 in. long, cut parallel to the bedding planes. In the water-sand case, the resistivity profiles revealed the existence of an extensive transition zone between flushed and uncontaminated zones. In the linear geometry of the experiment, the width of the transition zone increased as the square root of the injected fluid volume. For the oil-sand case the core was prepared by displacing the formation water with kerosene to minimum water saturation. During the subsequent invasion experiment. oil saturation was measured directly by means of an oil-soluble radioactive tracer, and resistivity profiles along the core were taken at the same time. These data were interpreted in terms of an oil-water front, followed by a formation water bank, a zone of mixed waters, and finally, invaded mud filtrate near the borehole. Micro-fingering and capillarity seemed to affect considerably the resistivity profiles observed in the invaded oil-sand experiment. Beyond the regular conductive annulus or "low zone", it was found that a resistive "anti-annulus" could also be formed. As a result of these experiments, some simplified invasion profiles have been accepted and are being used in Grand Slam* interpretations. INTRODUCTION The importance of the mud filtrate-invaded zone in interpreting electrical logs has long been recognized.',* In trying to account for its effect, only very simple models of the resistivity profiles in the radial direction from the borehole have been used. In fact, most log interpretation charts have been based on resistivity models consisiting of two media of uniform resistivity (R, and R,) abruptly separated at the diameter of invasion. Such a clean separation of the media of different resistivities seems unrealistic, since flushing may not be perfect and may vary with radial distance into the formation.3** The nature of the transition zone, when it is within the radius of investigation of the surveying devices, may affect the log readings. Campbell and Martin' verified that a conductive annulus containing a high percentage of formation water may be formed when mud filtrate invades an oil-bearing sand. Interpretations which are to include the effect of such an annulus require the addition to the model of a conductive zone located at the outer rim of the invaded zone.' Using the Buckley-Leverett relations,6 aturation profiles may be derived, from which resistivity profiles can be calculated. Results of such computations by K. S. Kunz and J. H. Moran were given in a paper by Dumanoir. Tixier and Martin,7 and led to the construction of log interpretation charts which were based on a representation with three media of resistivities R, R0 and R1. Fig. 1 shows a schematic representation of a resistivity profile which includes an annulus. Campbell and Martin realized that, during the invasion of an oil sand, both capillarity and mixing would contribute to rounding of the profile shown in Fig. 1. Capillarity tends to draw some of the formation water from the annulus into the uncontaminated (Rt) zone, whereas mixing of the mud filtrate with formation water of the

Jan 1, 1965

By W. D. Robertson, A. S. Tetelman

The technique of decorating dislocations was employed to investigate deformation and fracture resulting from Precipitation of hydrogen in Fe-3 pet Si single crystals. It is shown that cracks are produced on (100) planes inside crystals, as a consequence of the precipitation of hydrogen gas, either when crystals are quenched from a hydrogen atmosphere at elevated temperatures or cathodically charged with hydrogen at room temperature. Plastic deformation in the vicinity of cracks, observed as arrays of decorated dislocations, is in conformity with the calculated stress distribution about a crack containing an internal pressure, and the observations provide information permitting a detailed analysis of the mechanics of crack growth. The fracture characteristics of crystals containing internal cracks were evaluated at 25o and -196°C and the results are related to the mechanism of hydrogen embrittlement in terms of the growth of preexisting cracks. HYDROGEN in bee iron or steel produces two characteristic changes in mechanical properties: I), a decrease in ductility (macroscopic strain at fracture) that depends on temperature and strain rate, and 2), spontaneous fracture under static load that depends on time and apparent stress. Resolution of these phenomena into the microscopic processes that combine to produce the macroscopic effects is especially difficult in the Fe-H system in which the active component cannot be directly observed and only maintained in equilibrium with great difficulty in the temperature and pressure range in which embrittlement phenomena appear. As a result of these complications, verification of the numerous hypotheses'-5 that have been proposed to explain the microscopic mechanism of embrittlement depends on self-consistency with measured changes in macroscopic properties that are averaged over the volume of a specimen. It is obviously important to obtain a more direct evaluation of the microscopic processes that combine to produce embrittlement. Accordingly, the present investigation was designed to identify and observe, as directly as possible, the microscopic effects of introducting hydrogen into a bee crystal. It was concluded from a previous investigation6 of X-ray line broadening, produced by introducing hydrogen into pure iron at room temperature, that the only effect that could be associated with the introduction of hydrogen was plastic deformation; in particular, dilation of the lattice was not observed, within ± 0.01 pet, and no evidence was found that could be interpreted to support the idea7'* that hydrogen occupies tetrahedral interstitial sites in the iron lattice. The absence of lattice dilation is consistent with the extremely small solubility of hydrogen in bee iron9,10 (0.015 at. pet at 900oC and 1 atm pressure), and the evidence of plastic deformation is consistent with the fact that hydrogen, introduced by cathodic charging, eliminates the carbon yield point.11-13 Following this investigation, the immediate problem was to devise a method by which plastic deformation could be observed directly. The technique employed by Hibbard and Dunn14 to observe the movement of dislocations during bending and subsequent polygonization of Fe-3 pet Si single crystals was adopted and modified for the present purpose to include the observation of dislocation arrays in the volume of the crystal, and their association with the fracture process. EXPERIMENTAL PROCEDURE Single crystals of a high purity Fe-3 pet Si alloy, containing 0.007 pet C, were grown in vacuum by

Jan 1, 1962