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By W. S. Ayres

I. Introduction. This cavern was discovered Oct. 32,1904, by Mr. Charles 8. Deutschman, in company with whom I made, May 29 to June 3,1905, at the request of Mr. Howard Douglas, Superintendent of the Canadian National Parks, the first exploration of it for the Canadian government. The results were stated in a paper, orally presented, with lantern-views from my photographs, at the British Columbia Meeting of the Institute, Victoria, B. C., July 5, 1905.* The present paper embodies also the results of a second examination, made Oct. 25 to 29, 1905. The accompanging map, Fig. 1, will serve as a guide to the following description. 11. Location. The cavern is situated at snow-line, at the head-waters of Cougar creek, on the west slopes of the Selkirks, about 2 miles north from Ross Peak water-tank, and 5.5 miles west from Glacier station, on the main line of the Canadian Pacific Railway. It was then reached by an arduous climb from the water-tank, up the ravine of Cougar creek, for 8,000 ft. (2,000 ft. of altitude) over rock- and snow-slides, and through a thick tangle of alders. But an easy and very picturesque trail has, during the past summer, been opened by the government from Glacier station, which is also a hotel of the railway company. Figs. 3, 3 and 4 represent views, not heretofore published, of the grand scenery of this region, so rapidly becoming the object of attraction to thousands of tourists from all parts of the world. These views, as well as those shown in Figs. 5, 6, 7, 8

Jan 1, 1908

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium' oxide to form

Jan 1, 1948

By R. H. Atkinson, R. N. Rhoda

An improved technique has been developed for the deoxidation of palladium with aluminum which is especially suitable for use in making small castings with an induction-melting and casting machine. The effect of various crucible linings on the efficiency of the residual deoxidizer and accompanying oxide film in protecting palladium against oxidation during remelting also has been examined; the preferred crucible lining consists of zirconia cement. THE objective of this work was to develop a simple method of deoxidizing induction-melted palladium which would be suitable for use by manufacturers of jewelry and other small castings. In a common method of deoxidizing torch-melted palladium a piece of aluminum foil is dropped on the surface of the molten metal. If a film is present, which is usually the case, it must first be removed by oxidizing the molten metal thoroughly because it would interfere with the entry of the aluminum into the melt. Removal of the film is probably facilitated by a mild fluxing action of the silica crucibles which are used for torch-melting. However, removal of an alumina film from molten palladium in the crucibles normally used for induction melting is a much slower process and it became necessary to modify the de-oxidation procedure. In the modified procedure the charge is simply melted and the desired amount of aluminum, crimped to one end of a tungsten wire, is plunged through the film into the palladium and the wire immediately withdrawn. The trace of tungsten which dissolves along with the aluminum can be avoided, if considered objectionable, by using a palladium wire. In view of the persistence of the alumina film under the conditions of induction-melting it also was decided to ascertain the efficiency of this film in protecting palladium against oxidation during repeated remelting and casting. Melting Equipment and Materials The equipment used for melting and casting consisted of an Ecco GC:6, 6 to 8-kva high-frequency converter and an Ecco M34B centrifugal casting machine. This unit is being increasingly used for making jewelry and dental castings and it also has been found useful in making exploratory melts of a variety of nickel alloys, for which purpose it is well suited on account of its speed of melting and economy of material. A description of the machine and its operation will be published elsewhere.' A common palladium jewelry alloy, 95.5 palladi-um-4.5 ruthenium (referred to as "palladium" in the trade), was selected for the deoxidation tests. It was available as melting stock which had been melted in air to free it from oxidizable impurities, and also as clean scrap from previous melts which had been deoxidized with aluminum. The latter was thought to be typical of clean "palladium" scrap to be found in a manufacturing jeweler's establishment and it is also similar to one brand of "casting palladium." By the same token, the oxidized melting stock corresponds to "casting palladium" after the latter has been melted and thoroughly oxidized: Pure aluminum wire (99.9 pet), 0.032 in. diam; 1 in. = 0.036 g. Scrap tungsten wire, 0.014 to 0.020 in. diam. Argon, commercial water-pumped; 99.9 pet pure Experimental Procedure Samples of about 50 to 75 g of the palladium alloy were melted in a crucible lined with a proprietary refractory alumina cement. Some charges were melted in air, others in argon. The oxidized melting stock was melted and solidified a number of times in order to remove as much oxygen as possible before deoxidizing, but this treatment was unnecessary in the case of scrap. In either case the metal was deoxidized with aluminum (0.01 to 0.05 pet) by the

Jan 1, 1959

By Arnulf Muan, D. P. Masse

PHASE relations in the system CoO-SiO2 have been determined as a basis for further investigations of thermodynamic properties of olivine solid solutions involving Co2SiO4 as a component. Previous data on the system CoO-SiO2 are incomplete or uncertain. Biltz and Lemke1 determined the melting point of cobalt orthosilicate as 1345°C , but Asanti and Kohlmeyer2 have later found a considerably higher temperature, 1420°C. The latter authors also studied melting relations of one mixture on the CO side and two mixtures on the SiO2 side of the orthosilicate composition and sketched a tentative phase diagram for a limited composition range of the system. However, no phase identification was carried out, and the authors left unanswered the question of the possible existence of a stable meta-silicate phase. Greig3 showed that a 90 wt pct SiO2-10 wt pct Co mixture at 1725°C consists of two immiscible liquid phases. The quenching technique was used in the present investigation. Mixtures of high-purity cobalt oxide ("Fisher Certified") and dehydrated silicic acid ("Baker Analyzed") were equilibrated in air atmosphere. The samples were then quenched to room temperature and the phases present were identified by microscopic and X-ray examination. The samples were kept in small envelopes made from thin (0.0004 in.) platinum foil. Thermodynamic data which have become available recently for Pt-Co alloys4 were used to check that the losses of COO from the oxide samples by alloying of cobalt with platinum in the present investigation were too small to change significantly the compositions of the oxide material during the equilibration. A vertical tube furnace with an 80 pct Pt 20 pct Rh resistance winding was used in runs up to 1510°C. Temperatures in these runs were measured with a Pt vs 90 pct Pt 10 pct Rh thermocouple calibrated against the melting point of diopside (CaMgSi2O6, 1391.5?C). The given temperatures as measured by this technique are estimated to be accurate to *5°C. Quench runs at temperatures above 1650°C were made with a modified Roberts and Morey5 strip furnace, using strip resistors composed of a 60 pct Pt-40 pct Rh alloy. Temperatures were measured with an optical pyrometer which was calibrated against the liquidus temperature of a mixture composed of 10 wt pct CaO, 90 wt pct SiO2 (1707°C). The temperatures measured with this technique have an estimated accuracy of +15°C. The results are shown graphically in Fig. 1. Only one intermediate phase, the orthosilicate Co2SiO4 with olivine-type structure, is stable in addition to the end members cobalt oxide and silica. The melting point of the orthosilicate was found to be 1415" ± 5°C. The metastilicate CoSiO3 is not stable at the temperatures of the present investigation. The two eutectic points in the system CoO-SiO2 where COO plus olivine, and olivine plus silica, coexist with liquid were found to be 72 wt pct COO and 1407°C and 63 wt pct COO and 1381°C, respectively. The melting point of cobalt oxide in air was taken as 1745?C, based on the previous data of Aukrust and Muan.6 Within limits of error (+ 5?C), identical eutectic temperatures to those determined in air were found when two representative mixtures were equilibrated at 1 atm O2 pressure and in an atmosphere of 84 vol pct CO2, 16 vol pct H2. This suggests that changes in oxidation state of cobalt in the condensed phases are not significant as far as their effect on the phase relations are concerned. This inference was substantiated by failure to detect7 any "excess oxygen" (i.e., oxygen in excess of that contained in Co2SiO4) in a sample of orthosilicate composition equilibrated in air 10°C above the liquidus temperature and subsequently quenched to room temperature. This work was carried out as part of a research program sponsored by the U.S. Atomic Energy Commission under Contract No. AT(30-1)-2781.

Jan 1, 1965

By Bernard K. Asdell

Georgia, a state seldom considered to be an important mineral producer, has one surprising feature-it is the nation's largest producer of kaolin. Kaolin is a highly important raw material in the paper, rubber, ceramic whiteware, paint and chemical industries. In 1965, more than 2.7 million tons of kaolin were produced in this state, a 150,000-ton increase over the preceding year, and production continues to climb. Strictly defined, the term "kaolin" applies to a group of hydrous aluminum silicates in which kaolinite is the predominant mineral. Kaolinite is inherently white, non-abrasive, chemically inert, and of a very fine particle size, ranging from sub-micron to 40-microns equivalent spherical diameter. An electron-micrograph of kaolinite is shown in Fig. 1. The particles finer than about 2 microns are thin, elongated plates, hexagonal in outline. The larger particles, coarser than 2 microns, are predominantly vermicular in outline with a foliated structure. Table I shows a typical chemical analysis of commercial, wet-processed kaolin compared to pure kaolinite.

Jan 11, 1967

By E. A. Gulbransen, K. F. Andrew

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2'21'44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

By Jack A. Crichton, Henry J. Gruy

This paper discusses methods used in the estimation of natural gas reserves and the general conditions under which the various methods are applicable. The factors used in estimating natural gas reserves are reviewed. Errors which have been found to occur frequently are listed. Introduction The estimation of natural gas reserves has become of paramount interest because of the increasing importance of gas in the nation's economy. Gas is a most desirable fuel, a fact substantiated by the continued rise in the market demand. In addition, new uses for gas are being developed by the chemical, plastic, and associated industries, and plants are being built to make gasoline from natural gas. These are a few of the factors contributing to the importance of the nation's natural gas reserves. With the increased importance of gas there is an increase in the need for reliable estimates of the magnitude and availability of natural gas reserves. These estimates are being used currently: (I) to determine which fields contain sufficient available reserves to justify the construction of pipe-line outlets to serve particular markets; (2) to design pipe lines necessary to serve those fields adequately;] (3) to determine the location of industrial and chemical plants; (4) to finance the development of gas properties, and the construction of gas pipe lines; (5) to determine fair and adequate depletion allowances and depreciation rates; (6) to justify applications for gas pipe lines before various regulatory bodies; (7) to determine the number of wells required to exploit the reserves most economically; (8) to aid in establishing values for the purchase or sale of gas properties, and for purposes of inheritance taxes; (9) to determine equities under unitized operations; (10) to provide a basis for calculating the economics of gas-cycling operations. History or Estimation of Natural Gas Reserves The natural gas industry in the United States had its beginning during 1826 when natural gas was used for lighting the city of Fredonia, N. Y. The first natural gas pipe line was a 25-mi]le wooden line constructed from hollowed logs, connecting West Bloomfield and Rochester, N. Y. There is no record of an attempt to estimate the gas reserve at West Bloomfield but an attempt was made to determine the capacity of the well by measuring the time required to 611 a large balloon. One of the earlier publications concerning estimation of natural gas reserves is the "Manual for the Oil and Gas Industry," published by the Treasury Department, United States Internal Revenue, in i9i9. The following methods of computing "gas depletion" are listed: (I) production decline of the gas well or property; (2) decline in open-flow capacity; (3) comparison with the life history of similar wells or properties, particularly those exhausted Art

Jan 1, 1949

By W. A. Backofen, D. Lee, F. S. Jabara

THE empirical character of plasticity analysis insures a continuing need for measurements of the yield surfaces of anisotropic materials. Recently, Wheeler and Ireland (W-I) proposed that an octahedral yield locus could be constructed on the basis of six Knoop hardness indentations. Such simplicity would have obvious appeal, if it led to consistently dependable results. In other recent work, a much more straightforward (and more tedious) method of measurement was used to establish all quadrants of the plane-stress yield loci for two substantially anisotropic titanium alloys.2,3 The same materials have since been reex-amined by the W-I method with results being reported here. A full description of the stress state under a Knoop indentor would be complex. In principle, however, this can be avoided in relating the hardness number to a plane-stress yield locus, by the expedient of superimposing the appropriate hydrostatic component on that state of stress. Six possible orientations of in-dentor on orthogonal (symmetry) planes, along (principal) coordinate directions, are illustrated in Fig. 1(0). Pictured in Fig. l(b) are normal-stress components nominally associated with indentation n: o2(H), directly proportional to the Khn in this case, together with By overlaying a hydrostatic tension, ah, that in general is equal to the stress state around the indentation is reduced to one of plane stress in the x-y plane for which the stress ratio is a The key step in the W-I yield-locus construction is to represent the Khn for any indentor orientation as a vector quantity on the octahedral plane. In the plotting, the vector is given as deviatoric stress components along the principal axes in the ratio , where represents the direction of the minor (width) diagonal and 1 that of the major (length) diagonal. There is no attempt by W-I to justify the 7/1, although it might be supposed that the value originates in the usual ratio of major to minor diagonals in a Knoop indentation of about 7/1. If that were its origin, the link to the deviatoric stress ratio would presumably be made by first taking 7/1 and then turning to the Levy-Mises equation for isotropic material: Interpreted in this way, the W-1 approach seems arbitrary and even contradictory. Yet it would still be favored by two circumstances: the deformation under a Knoop indentor approaches plane strain: when dcw/del =a; and the shape of the locus where plane strain is represented is not overly sensitive either to the exact value of dc,/dcl or to the degree of anisotropy, within a rather wide range of both variables. The second point is illustrated below, after a few additional comments on applying hardness

Jan 1, 1968

THE discussion of this topic at the Open-hearth Conference at Detroit on Nov. 3, 1927, was opened by statements of the general principles involved, made by manufacturers of molds. Because of their general interest they are printed below. WILLIAM HAIL RAMAGE,* Hubbard, Ohio.-I did not come prepared to read a paper, thinking. the most I would be called upon to do would be to make a few, remarks by way of discussion. A number of our friends have pre-viously asked questions. similar to this which really does not permit a direct "yes" or "no" answer. If I may he pardoned for so doing, I believe it advisable to discuss rather what we consider the principal factors which in-fluence mold life. I think possibly a little undue weight has been given to the subject of the analysis of the metal. For the last eight years we have spent a lot of time, effort, and money investigating this very problem from a chemical, physical and microscopic standpoint. We have had the benefit of complete records and history of over 100,000 molds in service at a variety of plants and over long periods of time. Obviously, I cannot be so specific that I should divulge information that is really a trade secret. In our opinion the principal factors influencing mold life are: (1) design of the mold; (2) process of manu-facture, including workmanship; (3) care in the steel plant or what might be termed "the use or abuse" in the steel plant; (4) the analysis of the iron and the physical con-dition of it. Under normal conditions these factors are of importance in the order named, although in specific cases they might be rearranged in any order you choose. For instance, the best mold made can be destroyed in one or two pours by subjecting it to certain conditions which are occasion-ally met in steel plant practice. Obviously, in that case, nothing else matters but that one item. On the other hand, I have seen molds made of such a terrible design that it was a foregone conclusion it would have to be broken after the second pour of the ingot to get it out. In that case, nothing but design mattered. As to the effect of process of manufacture, let me cite a case. Some years ago there were two batches of molds sent to a certain company. They were the same sized molds, used under the same conditions and in the same kind of service. There were, 20 molds in each batch. The second batch sent gave ten times the life of the first batch. It is true that the design was changed a little, but not very much, and it was not. a bad mold to begin with. It is possible that the iron may have been better in the second consignment but not very much. In my opinion, it is con-servative to say that of the 900 per cent improvement in life, 5 per cent was probably due to better iron, 25 per cent to better design and the remaining 870 per cent to process of manufacture and workmanship.

Jan 2, 1928

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The Blast Furnace Studies Section, Metallurgieal Division, Bureau of Mines, has been working for several years on the mechanism of desulphurization of iron and steel by slags. The usual assumption that desulphurization takes place by diffusion of FeS from metal into slag and subsequent reaction of this FeS with CaO to produce CaS has seemed to us inconsistent with a number of experimental results we have obtained. We undertook, for example, to determine the proportion of sulphur in a slag present as FeS. An entirely satisfactory method of doing this has not yet been evolved. The results of extraction with metallic antimony led to an interesting conclusion, however. FeS is readily soluble in metallic antimony, either physically or by chemical reaction. On the other hand, CaS was found to be insoluble. Hence it would appear that by rapid extraction of the slag with antimony we might expect to determine the distribution of sulphur between iron and calcium. The results showed that much of the sulphur was present as FeS. In some instances the extraction of sulphur as FeS was almost quantitative. For example, in a slag containing 3.8 grams Fe and 3.7 grams S, extraction removed 1.18 grams S and 2.12 grams Fe. If all the iron present in the antimony had been FeS, 1.21 grams S would have been extracted. In another slag with 8.6 grams Fe and 0.06 gram S present, 0.14 gram Fe and 0.08 gram S were extracted. This was obviously extraction of sulphur as FeS within the analytical error and showed that FeS was present either in solution or as a dispersion. Attempts to determine the solubility of FeS and CaS in slag by quenching and ultramicroscopic investigation have indicated that the solubility of FeS is very low, and that reactions in the slag are probably not to be considered as homogeneous. A more detailed report on these theoretical considerations will be made at a later date.

Jan 1, 1940

By W. F. Holbrook, C. E. Wood, E. P. Barrett

The Blast Furnace Studies Section, Metallurgieal Division, Bureau of Mines, has been working for several years on the mechanism of desulphurization of iron and steel by slags. The usual assumption that desulphurization takes place by diffusion of FeS from metal into slag and subsequent reaction of this FeS with CaO to produce CaS has seemed to us inconsistent with a number of experimental results we have obtained. We undertook, for example, to determine the proportion of sulphur in a slag present as FeS. An entirely satisfactory method of doing this has not yet been evolved. The results of extraction with metallic antimony led to an interesting conclusion, however. FeS is readily soluble in metallic antimony, either physically or by chemical reaction. On the other hand, CaS was found to be insoluble. Hence it would appear that by rapid extraction of the slag with antimony we might expect to determine the distribution of sulphur between iron and calcium. The results showed that much of the sulphur was present as FeS. In some instances the extraction of sulphur as FeS was almost quantitative. For example, in a slag containing 3.8 grams Fe and 3.7 grams S, extraction removed 1.18 grams S and 2.12 grams Fe. If all the iron present in the antimony had been FeS, 1.21 grams S would have been extracted. In another slag with 8.6 grams Fe and 0.06 gram S present, 0.14 gram Fe and 0.08 gram S were extracted. This was obviously extraction of sulphur as FeS within the analytical error and showed that FeS was present either in solution or as a dispersion. Attempts to determine the solubility of FeS and CaS in slag by quenching and ultramicroscopic investigation have indicated that the solubility of FeS is very low, and that reactions in the slag are probably not to be considered as homogeneous. A more detailed report on these theoretical considerations will be made at a later date.

Jan 1, 1940

By C. E. Wood

THE Blast Furnace Studies Section, Metallurgical Division, Bureau of Mines, has been working for several years on the mechanism of desulphurization of iron and steel by slags. The usual assumption that desulphurization takes place by diffusion of FeS from metal into slag and subsequent reaction of this FeS with CaO to produce CaS has seemed to us inconsistent with a number of experimental results we have obtained. We undertook, for example, to determine the proportion of sulphur in a slag present as FeS. An entirely satisfactory method of doing this has not yet been evolved. The results of extraction with metallic antimony led to an interesting conclusion, however. FeS is readily soluble in metallic antimony, either physically or by chemical reaction. On the other hand, CaS was found to be insoluble. Hence it would appear that by rapid extraction of the slag with antimony we might expect to determine the distribution of sulphur between iron and calcium. The results showed that much of the sulphur was present as FeS. In some instances the extraction of sulphur as FeS was almost quantitative. For example, in a slag containing 3.8 grams Fe and 3.7 grams S, extraction removed 1.18 grams S and 2.12 grams Fe. If all the iron present in the antimony had been FeS, 1.21 grams S would have been extracted. In another slag with 8.6 grams Fe and 0.06 gram S present, 0.14 gram Fe and 0.08 gram S were extracted. This was obviously extraction of sulphur as FeS within the analytical error and showed that FeS was present either in solution or as a dispersion. Attempts to determine the solubility of FeS and CaS in slag by quenching and ultramicroscopic investigation have indicated that the solubility of FeS is very low, and that reactions in the slag are probably not to be considered as homogeneous. A more detailed report on these theoretical considerations will be made at a later date.

Jan 1, 1939

By Donald L. Johnson

REVIEWS on the applications of optical ellipsometry to the study of polycrystalline metal surfaces and oxidation-corrosion processes have been presented by Kruger and Hayfield, and white.' In view of the ability of this method to measure differences in film thicknesses to below 10A, ellipsometry was used to study nitrogen chromium surface reactions during the early stages of growth. Chromium specimens in the form of a vapor-deposited film on glass substrate were exposed to purified nitrogen for selected time increments at 700°F. This temperature was selected because it gave the best combination of exposure time and thickness change. Ellipsometer readings were taken immediately after exposure to determine polarizer and analyzer angles using monochromatic light at 5000A.2 After each set of readings was obtained, the specimens were exposed for an additional increment of time in nitrogen and a new set of readings taken. Film thickness was computed from LUCy's3 equation for nonabsorbing thin films. In Lucy's derivation, two equations for computing thickness were obtained. Peterson and Bashara4 have discussed the validity for using one of these equations when an independent value of the refractive index is used. The film was assumed to be Cr2N (Ref. 5) and was determined to be optically isotropic. Optical isotropy was determined by rotating the films about the surface normal and noting that the azimuth and phase difference did not change. Since Cr2N is reported to be hexagonal, it is assumed that optical isotropy results from randomly oriented grains of very small size. The thickness was computed using refractive indexes varying from 1.6 to 2.0. The maximum variation in computed thickness over this range for a given exposure was 20 pct. The data reported are based on a refractive index of 1.8. Reference readings on the metal surface were taken just prior to nitrogen exposure. No attempt was made to deoxidize or denitride the metal surface after vapor deposition, although specimens were observed to gain approximately 2A per day in air at room temperature. Twelve experimental exposures were made on a single sample over a total accumulative time of 132 min. Additional experiments over longer time intervals were made to determine the effect of heat up and cool down during and after exposure. As a result of these experiments, the thickness computed for each exposure was increased by 4A. Time profiles based on the linear law are similar to the oxidation profiles for many metals.' The rate of accumulation of the nitride film is rapid at first and slows down as the film thickness increases. The parabolic law x2 =k1t +k2 [11 gives a straight line in Fig. 1; therefore, it is concluded that the kinetic behavior is parabolic. Sey-bolt and Haman5 reported similar results for CrlN on chromium at 1000°C although the order of the thickness was much greater (10-3 cm). Analysis of thickness data based on other values of refractive index shows that the curves are shifted vertically but retain the same shape. According to Mott,7 it is expected that for thin films k2 is zero in Eq. [I]. Since the plot in Fig. 1 is linear through the origin, k2 is zero and the parabolic nature of the film growth is further indicated. The parabolic rate constant, calculated from the slope in Fig. 1, is 4.4 x 10-16 sq cm per sec. The corresponding work (+) required to bring an electron from the metal into the oxide is estimated to be 1.5 ev.7 The author thanks professor N. M. Bashara and D. W. Peterson, Electrical Materials Laboratory, University of Nebraska, for making the ellipsometer available and providing technical assistance. The Electrical Materials Laboratory is supported by the office of Naval Research, NONR 3718 (01). This work was partially supported by the Engineering Experiment Station and the Mechanical Engineering Department, University of Nebraska.

Jan 1, 1967

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By D. J. Coolidge, H. L. Sheakley

THIS paper does not deal with all sands used in the glass industry in Missouri; it covers only that used in the plate-glass factory at Crystal City. However, it is probably safe to say that other sands, pro- [ ] duced throughout the state for this purpose, are of identical nature. The glass sand used in Missouri is commonly called the St. Peter deposit, which is ascribed to the Ordovician Rock series in the form of sandstone. This St. Peter deposit, aside from a few small outliers, covers a large area of eastern Missouri. It forms, through a broad curve, the northeast margin of the typical Ozark region between Cape Girardeau on the southeast and Mineola, Montgomery County, on the northwest. The belt is extremely irregular, varying from one to ten miles in width; its length is 150 miles in a straight line. [ ] The outcrop near the entrance to the Crystal City mine appears in the form of a sandstone bluff approximately 30 ft. high, running along Plattin Creek (Fig. , I). Above the sand rock an overburden of Joachim limestone appears, which, thickens to nearly 300 ft. and forms the hill commonly called Buck Knob. Test holes, where drilled at various points and the drillers' log indicate that the St. Peter deposit ranges in thickness from 63 to 71 feet. PROPERTIES OT THE ST. PETER SAND From an analysis of the glass sands of the St. Peter formation in Missouri, the follow-

Jan 1, 1942

By J. R. Low, M. B. Reynolds, L. O. Sullivan

The effect of neutron bombardment upon the stability of type 347 austenitic stainless steel has been investigated by a magnetic technique. The relation of the ferrite content of a stainless steel to its magnetic properties is given, and an apparatus suitable for the measurement of the ferromagnetic saturation induction of small specimens is described. Results of measurements on irradiated specimens are tabulated. Exposure to a neutron flux was found to cause a slight increase in the ferrite content of type 347 stainless steel, the change increasing with increasing length of exposure and with increasing initial ferrite content. The similarity of the effect of irradiation to the effect of annealing is pointed out. Possible effect of irradiation upon density of austenitic stainless steel is discussed. COMMERCIAL austenitic stainless steels are alloys of iron, chromium, and nickel, plus small quantities of other elements. Although these alloys are normally used in the austenitic condition, this state is thermodynamically metastable at ordinary temperatures and transformation to a more stable state takes place under favorable conditions. In the austenitic state, these stainless steels have the face-centered-cubic crystal structure characteristic of y iron, but the stable state at room temperature is a mixture of austenite and body-centered-cubic ferrite. The transformation from the pure austenitic condition may be brought about by cold working the alloy at a temperature below that at which the aus- tenite becomes thermodynamically unstable (about 400°C), the completeness of transformation increasing with increasing severity of cold work and decreasing temperature. The behavior of the austenitic stainless steels under ordinary conditions of use is rather well known. However, use of these alloys in a nuclear reactor introduces a new variable: the effect of neutron bombardment upon the transformation from the austenitic to the ferritic state. It was with this in mind that a study of the radiation stability of austenitic type 347 stainless steel was undertaken. Magnetic Technique for Ferrite Determination Commercial austenitic stainless steels such as type 347 undergo little transformation under normal conditions of fabrication and use. In view of this fact, it seemed likely that neutron irradiation would change the ferrite content of the alloy but little. The method chosen for measurement of the effect of neutron irradiation was thus limited to one which would be quite sensitive to small changes in the ferrite content of the alloy. Of the properties of the stainless steel which can be measured, the magnetic characteristics are most sensitive to the quantity of ferrite present.

Jan 1, 1956

By H. Merton Ruth

THE northern anthracite fields, although facing the same economic problems as the southern fields, are confronted with the additional problem of fast dwindling reserves of anthracite which can be conventionally and economically won. The mining of coal which remains in thin beds and the recovery of pillars from areas heretofore considered unrecoverable, either by reason of cost or surface restriction, pose problems of in- creasing importance to the economic life of the northern field operations. Successful approaches have Been made to this problem and other work is being performed that holds promise. There exists in the northern anthracite field millions of tons of solid coal, the recovery of which has not been too successful due to the following inherent operating faults: inability to concentrate producing areas; the great quantities of rock to be cut and handled, lack of consideration of proper sequence and speed of second mining, and the continued use of the mine car as the basis of payment. A mining system that has successfully solved these major problems has been in operation in the Scranton area since 1944. Over 1% million tons have been produced from veins varying from 3 to 4% ft thick by this method, which is known as the multiple panel-triangular system-conveyor mining.

Jan 1, 1950

CHARLES G. ROEBLING Charles Gustavus Roebling, president of the John A. Roebling's Sons' Co., of Trenton and Roebling, N. J., and of the New Jersey Wire Cloth Co., of Trenton, and vice-president of the John A. Roebling's Sons' Co., of New York, died at his home, No. 333 West State Street, Trenton, on Oct. 5, 1918. Mr. Roebling, who was born in Trenton, was a son of the John A. Roebling who finished the plans for the Brooklyn Bridge just before he died. The bridge was completed by his sons, Charles G. Roebling and Col. Washington A. Roebling. Upon graduation from the Rensselaer Polytechnic Institute in 1871, Charles Roebling became associated with the Roebling company as a mechanical engineer. He was engineer and builder of the suspension

Jan 12, 1918

By F. L. Holderreed

A choosy in what they would smelt. The furnace charge had to be coarse, and it had to be rich. They discarded fines in excess of about 1/10 the total weight. They wanted 10% copper content and fussed about anything with as low as 5%. They concentrated the copper content of the charge as much as they could by prior selection. They roasted off enough sulfur to further enrich the copper content of the succeeding fall of matte (a melt of cuprous and ferrous sulfides or Cu2S.FeS). Then they desulfurized the iron and fluxed it by carefully adding silica (quartz, not silicates) for a slag of lower density than the cuprous sulfide (Cu2S or white metal). After skimming off the slag, they further desulfurized the white metal by blowing the molten bath with compressed air. The result was blister copper. Yesterday Their techniques and furnaces? Some experimented with mechanically rabbled roasters, but their standard roasting practice was burning coarse sulfide ore in 250-ton heaps. These heaps, approximately 24 x 24 x 6 ft, were burned for about 75 days down to 6-10% sulfur. The turnaround time for a given roasting position was 100 days. Assuming the base was a hearth, the calculated rate of treatment was on the order of 0.004 tpd per sq ft.

Jan 1, 1971

By P. Martinez, A. F. Hoyte, F. E. Senftle

The possibility of applying a neutron activation technique for silver exploration is considered. A mobile positive-ion accelerator type neutron source is used to irradiate a small area of rock or soil in situ. By using a short period of irradiation and gamma ray spectral analysis, a technique is shown for silver exploration. Two different mobile units are described. Laboratory and preliminary field tests both indicate that a sensitivity of less than 1 oz of silver per ton of ore can be achieved. The increasing consumption of silver for industrial uses and also for coinage has caused a serious shortage of silver in this country. The silver shortage has been reviewed and analyzed by kiilsgaard1 who concludes that, "The best hope for meeting future demands for silver is through accelerated exploration for precious ores." As almost all the exposed "bonanza" type silver deposits evidently have been found, it is urgent that some sensitive geophysical technique be found to detect large, extended, but generally low-grade, secondary ores, as well as hidden vein deposits. Silver is easily made radioactive by exposure to slow neutrons; hence a neutron activation method appears promising for locating silver deposits. The principles of mineral beneficiation using neutron activation techniques were discussed some years ago.2-4 Using the same approach, a preliminary description5 has been published of neutron activation as a mineral exploration tool. An exploration technique is described in which silver is made radioactive in situ and detected with a gamma radiation counter. The technique is similar to the well-known method used for uranium exploration. THEORETICAL CONSIDERATIONS Elemental silver consists of two isotopes, Ag107 and Ag109, having naturally occurring isotopic abundances of 51.4% and 48.6%, respectively. For short periods of irradiation of silver by thermal neutrons, the long-lived 250 day, half-life isotope, Ag110m, is not produced in significant quantities. However, significant quantities of 2.3 min half-life Ag108 and 24.5 sec half-life Agl10 are formed by the following reactions. Ag108 and Agl10 emit a 0.44 Mev (million electron volts) and a 0.66 Mev gamma ray, respectively. Ag107 + n + Ag108 (2.3 min) Ag109 + n + Ag110 (24.5 sec). Because of the large capture cross section (110 barns) of Ag109, and short half-life of Ag110 (24.5 sec), the 0.66-Mev gamma ray is the most prominent emission from silver for neutron activation periods of about a minute's duration.* The 0.44-Mev gamma ray from Ag108 will also be present, but will be one or two orders of magnitude lower in intensity. The decay scheme of Ag110 is shown in Fig. 1. If the neutron irradiation time is limited to about 100 sec, the Ag110 activity will essentially reach saturation and can be used to detect the presence of silver. In a neutron flux of 10 8 neutrons/cm2/set, the induced 0.66-Mev activity in 1 g of silver will be about 2 x 107 disintegrations per sec. This is about 1000 times the measurable gamma activity of 1 g of uranium in equilibrium with all its decay products; hence there is ample activity for detection. Under the same conditions of activation, most of the other elements do not reach this relatively high disintegration rate. Although this is in favor of the proposed technique, other problems must be considered. For mobile operation, it is desirable to obtain the largest neutron flux to weight ratio. Hence we have used a small 150-kev accelerator-type neutron source rather than an isotopic source such as an americium-beryllium neutron source. By use of remote control system, an accelerator-type neutron source can be safely used without the massive shield required for an isotopic source. Moreover, an accelerator-type source is more versatile in that it allows one to use a flux of either 14-Mev or 3-Mev neutrons, depending on whether a tritium or a deuterium target is used. With a 14-Mev generator, one can obtain a flux of 10 9 neutrons/cm 2/sec, and with a 3-Mev generator, the flux is generally two orders of magnitude less. Although silver will become activated with either generator using proper moderation, detection may be

Jan 1, 1968