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By Frederick N. Rhines, Robert F. Mehl

IT has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick's law (equation 1 below), ‡ in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick's law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Zedele and of Zedele.§ These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a singles olid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970

By Grover R. Castle

INTRODUCTION "Project Financing" or "Project Loans" have become increasingly popular in recent years, and commercial banks are being asked to consider more and more of such financing. However, the analysis of this type of loan is quite different from the analysis of a loan to a financially sound corporation based on the company's balance sheet. For this reason Chemical Bank did a study of project loans in an attempt to be more sophisticated in our approach to them. As part of this study, we examined 29 project financings for which information was available. In this article I shall describe project loans and set forth the guidelines we developed, as an aid to credit officers who might have occasion to analyse this type of financing. DEFINITION OF "PROJECT FINANCING" OR "PROJECT LOAN" The terms "project financing" and "project loan" commonly describe the various methods that banks and institutional lenders use to finance the construction of new projects on a basis whereby payout is anticipated from the revenue stream generated by the project. A project financing often involves a loan to a new entity formed specifically to own the project. The analysis of a project loan proposal is quite different from the analysis of other term-loan proposals since it involves a credit decision based on the review of a projection or forecast rather than of historical earnings and/or it involves the reliance on contractual obligations of third parties. Lenders are asked to assume the added risks associated with project loans because: 1. Project financing may permit a company to obtain additional leverage. It is possible for companies to arrange financing on a project basis that could not be arranged as a direct borrowing. For example, a company may not be permitted to borrow more money directly, due to a limitation in a bond indenture. However, a project financing can sometimes be negotiated on a basis not prohibited by the indenture. 2. Often the sponsors of, or the stockholders in, the project are seeking an off-balance-sheet financing. For example, 11 of the 29 projects in our study were arranged on an off-balance-sheet basis and one showed on the balance sheet as a deferred income item. An off-balance-sheet financing, for the purpose of this article, is a financing which does not show as a direct liability on the balance sheet of the sponsors of or stockholders in a project. 3. Projects are often located in a foreign country. The financing is arranged so that the lenders assume the political risk on the loan because many companies rightly believe that this arrangement affords a degree of insulation from political risk not otherwise obtainable. 4. Many projects are jointly owned by several sponsors. This form of financing lends itself well to a situation where a new entity is formed to own a project and do the borrowing. Project loans can be used to finance a variety of activities including development of iron-ore deposits and associated pelletizing plants; development of coal reserves; construction of pipelines, alumina plants, fertilizer plants and refineries; etc. The specific areas of analysis can be quite different, depending upon the type of project being financed. It is important, therefore, to classify the proposal according to the type of project, and also by the nature of the financing - nonrecourse financing, financing covered by a guarantee of completion and financing supported by an undertaking lasting for the life of the financing. I will discuss each of these types in more detail later, but first, I should like to make some

Jan 1, 1985

By W. F. Holbrook, T. L. Joseph

The problem of sulfur control is important in all blast-furnace operations but particularly for certain grades of steel because of the rigorous specifications. During the past decade the tendency has been to produce pig iron and hot metal of lower sulfur content. As most of the sulfur in the iron originates in the fuel, the use of high-sulfur coke demands modifications in practice to meet sulfur specifications. While it is generally known that high temperatures and more basic slags favor desulfurization, operators as a rule produce the most acid slag that will permit proper desulfurization. The viscosity of blastfurnace slag has been thought to be related to desulfurization and has been investigated by Feild and Roysterl, also McCaffery and his associates*, but apparently no systematic effort has been made to determine the relative desulfurizing powers of slags over the range of composition encountered in practice. Development of Testing Method Because slag and metallic iron are immiscible, the desulfurization reaction is heterogeneous, occurring only at the interfaces between slag and metal bodies. In the blast furnace the newly reduced iron, containing FeS, descends through the slag bath probably either as small drops or streams, at the interfaces of which desulfurization occurs. After its descent through the slag the iron collects to form a bath of metal, at the top surface of which desulfurization reaction probably occurs. These two steps have been thought to account for all desulfurization in the blast furnace. Kinney3 found that metal removed from the blast furnace just above the tuyeres contained three to four times as much sulfur as the iron at cast. Herty and Gaines4 conclude that most of the sulfur is removed while the metal is passing through the slag. Mund, Stoecker

Jan 1, 1936

By W. F. Holbrook, T. L. Joseph

The problem of sulfur control is important in all blast-furnace operations but particularly for certain grades of steel because of the rigorous specifications. During the past decade the tendency has been to produce pig iron and hot metal of lower sulfur content. As most of the sulfur in the iron originates in the fuel, the use of high-sulfur coke demands modifications in practice to meet sulfur specifications. While it is generally known that high temperatures and more basic slags favor desulfurization, operators as a rule produce the most acid slag that will permit proper desulfurization. The viscosity of blastfurnace slag has been thought to be related to desulfurization and has been investigated by Feild and Roysterl, also McCaffery and his associates*, but apparently no systematic effort has been made to determine the relative desulfurizing powers of slags over the range of composition encountered in practice. Development of Testing Method Because slag and metallic iron are immiscible, the desulfurization reaction is heterogeneous, occurring only at the interfaces between slag and metal bodies. In the blast furnace the newly reduced iron, containing FeS, descends through the slag bath probably either as small drops or streams, at the interfaces of which desulfurization occurs. After its descent through the slag the iron collects to form a bath of metal, at the top surface of which desulfurization reaction probably occurs. These two steps have been thought to account for all desulfurization in the blast furnace. Kinney3 found that metal removed from the blast furnace just above the tuyeres contained three to four times as much sulfur as the iron at cast. Herty and Gaines4 conclude that most of the sulfur is removed while the metal is passing through the slag. Mund, Stoecker

Jan 1, 1936

By A. M. Gaudin

A GREAT number of hypotheses has been advanced to explain the complex phenomena that are encountered in flotation. In the days of bulk-oil flotation, when a large quantity of oil was employed, it was observed that the oil-mineral aggregate floated above the ore-pulp because of its lesser density. With the advent of froth-flotation this phase of the theory had to be modified to take into-account the presence of air bubbles.. The reason why the mineral-bearing froth of today rises to the top of flotation cells is, of course, because the air-mineral aggregate, with whatever reagent may be associated with it, is lighter than the pulp. In an attempt to explain froth-flotation the fact has been emphasized that certain minerals are wetted and therefore remain in water; while others are not wetted and therefore become associated in preference with air. Such an "explanation" does not explain facts, it merely states them; for instance, it does not explain why minerals are wetted under some circumstances and not wetted under others. Going somewhat further, the wetting or nonwetting of minerals by water has been ascribed' to differences in the angles of contact between oil droplets and mineral surface at the surface of the minerals. This explanation, however, was abandoned when soluble flotation reagents came to replace the so-called "insoluble" reagents. Another theory, sponsored about 10 years ago by Ralston,2 involves the effects of electric charges at the surface of the mineral particles and air bubbles. This theory, unfortunately, was not developed as fully as it seems desirable. The belief that adsorption phenomena might play a preponderant role in flotation3 has been rather widespread for the last 10 years. Unfor-

Jan 1, 1928

By E. A. Gulbransen, J. W. Hickman

INTRODUCTION DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may occur to such a degree that oxides may form in the body of the film and on the outer surface which are different from those that would normally form if the additional elements were not present. The use of transmisson electron diffraction may aid us in interpreting these phenomena. Up to the present time all of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physical state of the alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the removal of carbon by oxygen in a decarburization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with

Jan 1, 1948

By George A. Packard

The experiments here described were made under my supervision while temporarily acting as head of the Department of Metallurgy at the Missouri School of Mines, at Rolla. The work was done by Messrs. W. E. Brown, W. C. Richards, and F. L. L. Wilson, and the description of the results forms a portion of a thesis presented for the degree of Bachelor of Science. These results are submitted because I have seen no description of the application of pot-roasting to the treatment of a copper-concentrate. This work followed that already described in the discussion of the Lime-Roasting of a Galena-Concentrate,' and was similarly occasioned by the lack of a furnace of the reverberatory type in which the copper-concentrates could be smelted. The material for the tests was a mixture of three lots available. The first consisted of 8-mm. ,jig-concentrates and the second of 0.5-mm. table-concentrates, from the San Juan district, Colo. Both contained pyrite, chalcopyrite, and galena. The third was a lot of copper-ore, found in the laboratory, which had been crushed through 8-mm. screen, and had at some previous time, before the laboratory roasting-furnace was torn down, received a partial roasting. The analyses of these ores are given in Table I. In order to determine the applicability of pot-roasting as to each lot of ore, and the effect of varying proportions of lime, six preliminary tests were made in a " size N " Battersea crucible, 9 in. high by 6 in. in diameter at top, with a 5/8-in. hole bored through the bottom. The crucible was set in the upturned elbow of a 2-in. pipe, the joint being luted with clay; and air was obtained from a receiver supplied by a compressor. The

Jan 1, 1908

By F. M. Simonds, E. Z. Burns

The Rawley property is located in the Kerber Creek mining-district, Saguache county, Colorado, at an elevation of 10,600 ft. (See sketch-map, Fig. 1.) Ore was found in this vicinity as early as 1880, and claims covering a large area were located and in many instances patented. The ores, however, being of comparatively low grade, and the nearest railway station, Villa Grove, being some 20 miles away, it is extremely doubtful whether any considerable amount of ore was ever handled at a profit. It is safe to say that several hundred thousand dollars were spent (a large part in building mills) previous to 1902-03. About that time a very capable promoter gathered together a group of these claims and interested some New York people, who had had no previous mining experience, in the purchase of these claims. Following the organization of a company, this promoter became General Manager. As often happens under such conditions, the first step was to erect a mill to treat 100 tons per day. It may not be fair to this enterprise to say that the failure which followed might have been foretold, simply on general principles, but this much is certain—the water supply fluctuates in the course of a season through a wide range and for a considerable portion of the year was inadequate to run this mill at capacity. Further, it is currently reported that some of the mill foundations were placed on ice. However true this statement may be, it is a fact that, when first inspected by us, many of the belts in the mill were held on'their pulleys by means of idlers. A shut-down followed, with a material re-adjustment of interests, at which time we became consulting engineers for the company.

Jan 1, 1914

By B. R. Banerjee

MATERIAL used throughout this investigation was high-purity aluminum (99.998 pct). The 1/2-in. cubes were cut out of a cold-rolled slab and annealed at 550°C for 1 hr before deformation. The single crystal specimen was 1 in. in diam x 0.33 in. thick, cut from a cylindrical crystal produced by cooling at about 55°C per hr in a furnace which had a convenient gradient of about 10°C in every 4.5 in. vertical crucible length. Specific data on the ten specimens studied are summarized in table I. Three types of deformation were employed: (I) compression in a hand-operated hydraulic press; (2) impact with a 7-lb sledge hammer; and (3) rolling, using a wedge-shaped specimen' to obtain a gradient of deformations varying from 0 to 50 pct along the length of the wedge. Specimens were either deformed at room temperature, or first cooled in a freezing mixture of dry ice and ether at a temperature of —72°C and then deformed between steel blocks cooled with dry ice. The specimens deformed at the low temperature were ground and polished through 000 emery paper and wheels impregnated with alundum and alumina No. 1. During this entire procedure the specimens were dipped frequently in the freezing mixture of dry ice and ether in order to maintain constantly a frosty surface as insurance against overheating. All specimens were given a final electrolytic polish, using two different electrolytes* to insure that the surface effects observed were not char- acteristic of the polishing technique. With both electrolytes, the annealed specimens gave even surfaces with good polish. Several standard etchants were tried without success. The best results were obtained with an immersion etchant, developed in this connection, containing: hydrofluoric acid, 4 parts; nitric acid, 1 part; glycerine, 3 parts. Discussion of Results Typical strain markings have been observed within deformation bands, as shown in figs. 1, 2, and 4. By stereographic plotting of metallographic measurements, the strain markings within a deformation band in a single crystal of aluminum deformed by compression were found to be traces of (111) planes within a maximum scatter of 6". The edges of the deformation band were found to be traces of the (100) planes also within the maximum scatter of 6" (in agreement with previous workers). At 30 pct deformation, this scatter was considered quite normal because of the fragmentation and rotation of the crystal. This solution, based on the traces on one plane of observation is not unique, but as the planes were observed to be those normally and logically to be expected, further work in this regard was not felt to be necessary. The study of strain markings in a wedge-shaped specimen, rolled to obtain a gradient of deformation from 0 to 50 pct, revealed prominent strain markings at 25 pct reduction in thickness (fig.5). Faint and weak strain markings were visually observable up to a minimum reduction in thickness of about 12 pct. Since strain markings have been observed in other face-centered cubic metals after much smaller deformations;1, 2 and since the rate of recovery in aluminum is high, it is believed that, at lower deformations, self-recovery removes the localized strains at the slip interfaces, thus removing the source of the etching effects that give rise to strain markings. At high magnifications, strain markings sometimes seem to appear as very thin, light-banded re-gions bounded by a pair of dark edges. This so-

Jan 1, 1951

By C. D. Broadbent

INTRODUCTION The slope stability research plan at Kennecott was developed to serve the specific needs of large, open pit mines; primarily those developed in faulted and highly-fractured intrusive deposits. The program emphasis is on applied research; being defined in this case as research into the engineering mechanics of discontinuous rock and into the related rock property survey and slope design techniques. The program has been developed in phases, with each phase organized to explore more thoroughly the most significant findings of previous work and to improve on techniques found to be applicable. The current work is based on principles developed early in the program and that show promise of having engineering and economic value. A brief summary of the conceptual principles of the program is given to put our current work in context. This is followed by a review of the two cooperative programs done with the U. S. Bureau of Mines. Most recent work is described and interpreted in terms of practical slope design. Although failure-free slopes are a desirable goal, it is recognized that some failures will occur when overall slope designs approach a calculated safety factor of one. A discussion of failure control research is therefore offered. BACKGROUND In 1965 Kennecott management specified that a slope stability technology must be used to achieve optimum development of ore resources. The subject was carefully explored and by 1960 it had been established that there was no technology readily applicable to open pit slope design. Therefore, in 1962, Kennecott Copper Corporation and the U. S. Bureau of Mines agreed upon a cooperative research program having the objective of developing a mine slope stability science. One of the first decisions made by the cooperating groups was that the research must be conducted primarily in the field and not in the unrealistic environments of a laboratory. Accordingly, the Kimbley Pit, an abandoned mine once operated by Kennecott's Nevada Mines Division in Nevada, was selected for the full-scale research. Fortunately, there was near-universal agreement on the basic stability parameters and thus on the areas to be investigated. These parameters were acknowledged to be: (1) anisotropy (generally due to faults or joints), (2) stress, and (3) water; in that order of importance.

Jan 1, 1972

By D. J. Weintritt, J. C. Cowan

Methods of studying oilfield mineral .scale deposition in the laboratory do not work for barium sulfate because only small nonadhering crystals ore formed. On the other hand, barium sulfate scale found in down-hole or surface equipment is strongly adhering and may contain very large crystals. Results suggest that most of the difference derives from the extremely low .solubility of barium sulfate. Firm adherence of scale and the consistent development of oriented crystals 100 microns and larger suggest a relationship between scale adherence and crysta1 growth. Data from this study indicate some reasons for barium sulfate's occurring as a deposit in oilfield waters. The unique characteristics as well as the associative properties of barium sulfate scale as related to calcium carbonate and calcium sulfate ere shown. INTRODUCTION The first observed deposition of barium sulfate scale in oilfield production equipment is unknown but probably coincides closely with the beginnings of the oil industry itself. Moore' described barite oolites in some producing wells in the Saratoga field, Tex., in 1914. Currently, positive identification of barium sulfate deposition is recorded in most of the major oil-producing areas of the United States. As efforts continue to identify the composition and functions of the materials found in scale deposits, the geographic and economic importance of the part played by barium sulfate will become even more important. This belief is based on the following Facts. 1. Many oil fields in the U.S. are in or entering their mature phase and the volume of produced water is increasing; thus, the cumulative effects of low-solubility minerals become more significant. 2. Secondary recovery techniques and increased emphasis on waste disposal systems require controlling the behavior of all constituents of water to prevent formation plugging. 3. The more general use of instrumental analysis has reduced the time and improved the accuracy of complete scale and water analysis. 4. Once formed, barium sulfate scale is resistant to present methods of chemical removal; therefore, costly mechanical methods are necessary. Thus, new methods of prevention and control will require specialized chemical techniques and better knowledge of the causes of scaling. Consider the results of some simulated field deposition studies illustrating this need (Fig. 1). The studies utilized a Scale Deposition Test Cell* and each coupon was exposed to 8,000 ml of a 300 me/liter solution of the various types of mineral scale. All tests were conducted at 140F. Only the calcium sulfate and calcium carbonate deposited scale. The solution containing 300 me/liter of barium sulfate exhibited copious amounts of precipitate, but none of the precipitate adhered. The fluids from the effluents were also allowed to impinge on glass slides. Fig. 1 shows the relative adherence of the three types of scale on unetched glass. The barium sulfate failed to deposit in the same manner as the calcium carbonate and calcium sulfate solutions.

By Leendert de Witte, Fred J. Radd

In many areas caring failures can be directly related to electrical currents observed in the casings. It is the thesis of this paper that the observed casing currents are mainly due to electrochemical potentials of the type in evidence on spontaneous potential curves of electrical logs. The general nature of these potentials are discussed and an equivalent circuit is given for current and potential distributions around open holes. The casing forms a short circuit to these potentials and tends to average the effects of local cells. The case of casing corrosion opposite the Dakota water sands in the salt-mud area of Kansas is discussed anil used us a qualitative, illustration of the relation between SP's and casing currents. A method of quantitative derivation of casing current distribution frorn electric log SP curves, using linear transform theory, is described and results are compared with a measured current profile. The effects of hydrogen over-potentials at the cathodic portions of the pipe are considered and some laboratory data are given in support of conclusions regarding the over-1.01tuge.s. INTRODUCTION To date an appreciable amount of work has been done on the measurement of oil well casing currents and on the correlation of the anodic portions of the current profiles with corrosive casing failures. Speculations on the origin of the casing currents have, however, remained rather vague; and although almost every plausible cause has been mentioned, there is to the writers' knowledge no clear-cut expose' on the details of the causes of the corrosive currents in the literature. A study of current surveys and casing failures in the N.W. Burnett field, Ellis County. Kan.. indicated the probability that concentration cell emf's between the Wellington salt section and the relatively fresh waters in the Dakota sands were a major cause of the corrosion currents. A more general concept evolved upon analysis of the severe corrosive conditions in the Pleistocene sands in the Ventura Avenue and San Miguelito fields in California. In this area no major variations in the salt content of the formation waters occur and yet large casing currents are observed. An explanation is found in the fact that the local spontaneous potentials which are set up due to concentration contrast between the drilling fluid and the connate water are short circuited when casing is set. The very conductive path through the casing increases the magnitude of the currents and has the tendency to average local sources over fairly large intervals. Current will flow between the sections that are predominently shaly and the sections that are mostly sandy. At the places where the current leaves the pipe, corrosive attack will occur. This same phenomenon will be present wherever unprotected pipe is set through sections that show large SP kicks on the electric logs over reasonably thick interval~. GENERAL- NATURE OF THE SPONTANEOUS POTENTIALS When a sequence of sedimentary rocks is penetrated by a drill hole filled with a mud which has a different salt concentration from that in the formation waters, various types of electrochemical potentials are established between the formations and different parts of the mud column. Opposite clean sand sections. a simple liquid-liquid junction potential will be observed; while opposite argillaccous formations, a membrane potential, often referred to as shale potential, will be established. The first quantitative analysis of these emf's in terms of liquid junction and membrane potentials is due to Wyllie.1

Jan 1, 1956

By J. N. Maycock, P. W. M. Jacobs

Previous measurements of the thermoelectric power of ionic crystals are reviewed briefly. It is concluded that, while extensive measurerements are available on systems in which the electrode M has a cation in cornon with the sall MX, there is as yet little modern work on systems in which the metal electrode M' does not haue a calion in common with the salt. We haue now measured the thermoelectric power of- single cryslals of KC1 and of KC1 + SrCl2 between plati.nu?n electrodes over a much wider range of temperature than before. individual ionic heats of transport, which, while probably not very accurate, are of a reasonable order of magnitude, are obtained from this data on the basis of an assumption that charge carriers do not cross the electrode/salt interface. RELATIVELY little work has been done on thermal diffusion in ionic crystals. Reinhold and coworkers1-I measured the thermoelectric power and Soret effect in silver and cuprous salts and their mixed crystals. One electrode was kept at constant temperature and electromotive force was measured as a function of the temperature gradient. This is not a satisfactory technique if the results are to be compared with theory; rather should the electromotive force be measured for small temperature differences as a function of the mean temperature of the two electrodes. They used electrodes having the same cation as the salt. Patrick and Lawsons measured the thermoelectric power of AgBr and of AgBr containing 0.25 mole pct CdBr2 using silver electrodes and temperature gradients of 10°C in the temperature range 100° to 400°C. The results were analyzed using the Teltow9 values of the ratio of the mobility of the two types of charge carrier (cation vacancies and interstitials) found from conductance measurements and the wagnerlo estimate of the heterogeneous contribution to the thermopower, Ohet They obtained values of qi = 0.017 ev and q$ = -0.385 ev for the heats of transport of interstitial Ag ions and cation vacancies, respectively. Their data has been reanalyzed by Haga using the corrections to the Wagner formula for ehet given by Howard andLidiard; Haga found ev. Christy et a1.14 have measured the thermopower of AgBr containing 0.01 to 1.0 mole pct CdBr,. They analyzed their results in terms of the theory of Howard and Lidiard and found that excellent agreement with the theory was obtained if q5 + : + hF was set equal to 0.70 ev at 175°C and equal to 0.58 ev at 250°C. Since Teltow's value for hF, the enthalpy of formation of a Frenkel defect pair, is 1.27 ev, this means that qt + q: increases in magnitude from -0.57 ev at 175°C to -0.69 ev at 250°C. This result is in poor agreement with Patrick and Lawson's value of -0.37 ev for pure AgBr (for which the corrections to the Wagner estimate for ehet are very small). christy1' has also reported thermopower measurements for pure silver halides and for the systems he finds that qr + qt for AgBr increases in magnitude from about -0.55 ev at 150°C to about -1.1 ev at 400°C. The temperature dependence of the sum of the heats of transport in AgCl is very similar in magnitude. The sum qi + q cannot be decomposed into the individual interstitial and vacancy heats of transport without a knowledge of the entropy contribution from the change in the lattice vibrational frequencies around the interstitial and vacancy. Despite this it seems an inescapable conclusion from Christy's analysis that and -6 = Q Ag are quite strongly temperature-de pendent and that -q: is much greater in magnitude than the corresponding activation energy for vacancy migration, +0.37 ev. It remains a mystery as to why the data for pure AgBr are fitted so well by the assumption of temperature-independent heats of transport if association of impurity ions and vacancies is neglected.l The values for q$ and q: so obtained are also much more in line with those expected from a simple kinetic interpretation of the heats of transport due to wirtz.17 Christy and Hsueh have also measured the thermopower of CuCl between copper electrodes; 0 for pure CuCl is comparable with that for the silver halides but, owing to the limited solubility of divalent cation impurities it was not found possible to deduce values for the heats of transport. In contrast to these extensive measurements on cells of the type M MX 1 M, there have been relatively few attempts to measure the thermoelectric power of cells of the form M' 1 MX I M'. (We specifically exclude from discussion cells of this type in which the metal electrodes M' are in contact with gas containing a controlled partial pressure of either M or X,, since in these cells the electrochemical reactions are analogous to those of the first type.) The thermoelectric power of Pb12, PbC12, TlC1, TlBr, TlI, NaNO3, and KNO 3 between platinum electrodes was measured by Thie1e.l3 In discussing these measurements Holtan20 asserts that the thermopotential initially fluctuated wildly and even changed sign before approaching a steady value. A high degree of irreproducibility is also evident in the work of Nikitinskaya and Murin21 who first studied the thermopower of NaCl and KC1 between platinum electrodes. Much better reproduci-bility was achieved in our earlier measurements on KC1;22 these were, however, confined to a relatively narrow temperature range and one of the objects of the work reported in this paper was to extend the temperature range of the measurements of the thermoelectric power 8 of KC1. The only other published

Jan 1, 1967

By K. A. Jackson, J. D. Hunt

A new classification of eutectics is proposed, based on tlze entvopies of wzelting of the tuio eutectic phases. The clnssification was used to predict suitable tvansparent analogs of the metallic systems. Experimental confir?nation loas obtained for the theovetical shape of the lamellar solid-liquid interface, fov the fault mechanisms of lanzellar spacing changes, and for the development of low-energy solid-solid boundaries between the lamellae. An explanation is presented to account jov the irvegular and coinplex regular structures zrhich are found in some eritectic systems. FrOM experimental observations, single-phase materials can be divided into two groups according to their solidification characteristics, those that grow as faceted crystals and those that do not. acksonl' showed from thermodynamic reasoning that the type of growth depended on a factor a which was almost thg entropy of melting. Most nonmetals have high entropies of melting (a greater than 2) and grow with crystalline facets. Most metals have low entropies of melting (CY less than 2) and grow almost isotropically with no facets. The authors propose that eutectics may be classified in a similar manner. There are three groups of eutectics, those in which both phases have low entropies of melting, those in which one phase has a high and the other phase has a low entropy of melting, and those in which both phases have high entropies of melting. Lamellar or rodlike structures are formed in systems in which both phases have low entropies of melting. In these alloys dendrites of either phase may be formed, when the alloy is rich in the relevant component. Examples are Pb-Sn, Sn-Cd, Pb-Cd, Sn-Zn, Al-Zn. Irregular, Fig. 14((), or complex regular, Fig. 14(b), structures are formed in alloys in which one phase has a high entropy of melting and the other has a low entropy of melting. Examples are A1-Si, Zn-MgzZnll, Pb-Bi, Sn-Bi. When the alloys are rich in the low entropy of melting phase, dendrites are formed; when the alloys are rich in the high entropy of melting phase, faceted primary crystals are produced. These crystals are sometimes called hoppers or pseudodendrites. In this work the term dendrite will only be used to describe nonfaceted primary crystals. Dendrites are not formed during solidification in high entropy of melting single-phase materials. The third group of eutectics includes alloys in which both phases have high entropies of melting. Each phase grows with a faceted solid-liquid interface. Since most metals do not have high entropies of melting, metallic examples in this eutectic group are rare. However they may occur between some intermetallics and semiconductors or semimetals such as silicon, germanium, and bismuth. Attempts have been made to study eutectic solidification visually by watching the growth process.374 Since metals are not transparent, the observations had to be made on external surfaces. This difficulty can be overcome by using transparent analogs of the metallic systems. As was mentioned earlier, most single-phase compounds have entropies of melting greater than 2 and so grow as faceted crystals. Recently organic materials with entropies of melting less than 2 were investigated.' These materials grow in exactly the same way as the low entropy of melting metals. When the materials are pure, they grow with a solid-liquid interface parallel to an isotherm; when they are impure, cells or dendrites are formed. Since these materials are transparent, have low melting points, and even have cubic structures, they should be ideal for making up transparent analogs of the metallic eutectics. The purpose of the present work was to investigate these organic eutectics and to see whether this quite different series of eutectics could be classified in the same way as the metallic systems. The observations made on the organic alloys are also discussed with reference to the current theories of lamellar growth. Explanations are proposed to account for the structures formed in the other eutectic groups. EXPERIMENTAL Thin cells containing the organic alloys were uni-direction ally solidified on a specially constructed microscope stage.' Uniform growth rates were obtained by moving the cells, with a motor drive, through a fixed temperature gradient, so that the solid-liquid interface remained stationary with respect to the microscope objective lens. The cells were made by fusing two microscope cover slides 7/8 by 7/8 by 1/100 in. together on three sides, leaving a gap of 1 to 3 mils between the slides, and these were filled by surface tension. A preliminary investigation of the phase diagram between two components could be made very rapidly. One side of the cell was filled with component A and the other side with component B. Since only a small amount of mixing could occur every composition from pure A to pure B was present in the cell. When the cell was placed in the temperature gradient a pictorial representation of the phase diagram was obtained. Eutectics, peritectics, "interorganics", and solid -solid transformations could be readily detected. Fig. 1 shows part of a eutectic phase diagram. The Sample was first grown slowly then stopped. The two

Jan 1, 1967

By Hugh O?Neill

IN PREVIOUS papers,1 the author has reported the results of experiments on the straining in tension of a single crystal test piece, about 0.6 in. long, of vacuum-melted electrolytic iron containing 1.8 per cent. of silicon. The crystal was originally in the "as cast" condition, and was stressed slowly along a tetragonal axis so that slipping along conjugate gliding planes finally transformed the original cylindrical portion into a pair of fracture wedges. One of these fracture wedges was sectioned along the stress axis in a plane at right angles to the edge of the wedge. A metallographic study of this plane of -section led to the conclusion that slip had taken place in the (111) direction along (112) planes making a V shape with the stress axis. The present paper describes the results of scratch-hardness tests conducted on the same section, in order to determine the distribution of strain hardness therein, followed by annealing, and considers the resulting variations in hardness. These observations supplement those made by Krivobok2 on similar material reduced 25 per cent. by hammering (i. e., by impact) in the cold. In order to investigate ageing effects, two small crystals of the same alloy were also tested.

Jan 1, 1928

By E. Miller, J. M. Eldridge, K. L. Komarek

Aclivilies of magnesium in liquid Alg-Si alloys have been delermined between 5 and 60 at. pcl Si, close to the melling point of Mg2Si, by an improved isopieslic melhod. Silicon specinrens, held in alumina crucibles and graplrile conlainevs of special design, were healed in a letrlpevalure gvadient and equilibrated with mag-nesilcrrl rapor in a closed lilanium system. The ther-madynamic Junctions were calculated and compared with the thermodyuamic properties of the other three mg- Gvoup IVB systems. Lattice paramelers of three Mg2X compounds were measured. The bonding in the Mg2X compounds is largely covalent with small and uarying amounts of metallic and ionic conlvibutions. The Mg-Si phase diagram1 has one congruent melting compound, Mg2Si, of essentially stoichiometric composition, two eutectics, and very limited terminal solid solubilities. Little information is available on the thermodynamic properties of this system. The free energy of formation of Mg2Si has been determined by the Knudsen cell technique2 in the range 572" to 680oC, by the transportation method3 between 858" and 950oC, and by the electromotive-force method4 in the range 400o to 600°C. Kubaschewski and villa5 and caulfield6 have measured the heat of formation of Mg2Si. An electromotive-force study of magnesium-rich liquid alloys was recently published by Sryvalin el al.7 The present investigation was undertaken to complete a general survey of the thermodynamic properties of the homologous series of Mg-Group IVB systems, i.e., Mg-Pb,a9,Mg-Sn,10,11 mg-Ge,12and Mg-Si. An isopiestic technique, previously developed for similar measurements on liquid Mg-sn11 and Mg-Ge alloys,12 was modified for the Mg-Si system. Specimens of the nonvolatile component, silicon, were contained in dense alumina crucibles placed inside covered graphite crucibles which were heated in a temperature gradient in an evacuated and sealed titanium reaction tube and equilibrated with magnesium vapor of known vapor pressure. The alumina crucibles prevented contact between the highly corrosive liquid Mg-Si alloys and graphite. The graphite cruci- bles effectively preserved the high-temperature equilibrium composition of the liquid alloys containing highly volatile magnesium on termination of the experiments during the quench to room temperature. EXPERIMENTAL PROCEDURE Silicon of semiconductor-grade purity (E. I. du Pont de Nemours and Co., Brevard, N.C.) and 99.99+ pct Mg (Dominion Magnesium Ltd., Toronto, Canada) were used. Graphite crucibles with press-fitted lids were machined from high-density (1.92 g per cu cm) rods (Basic Carbon Corp., Sanborn, N.Y.) which had a maximum ash content of less than 0.04 pct. The alumina crucibles had a purity of 99.7+ pct (Triangle RR grade, Morganite, Inc., Long Island City, N.Y.). In preliminary runs the liquid alloys were contained in graphite crucibles following the exact procedure developed for the Mg-Ge system.'2 These runs failed due to appreciable reaction between the molten Mg-Si alloys and graphite, and the results have been discarded. The procedure was then modified and the Mg-Si alloys were subsequently held in alumina crucibles. For most of the runs alumina crucibles of known weight and approximately 6.3 mm ID, 12.5 mm height, 1.0 mm wall thickness were loaded with weighed amounts of silicon and encapsuled in tightly covered weighed graphite crucibles 5/16 in. ID, 2 in. helght, 3/32 in. wall thickness). The graphite crucibles were machined from rods which were 85 pct of the theoretical density. These crucibles were therefore sufficiently porous so as to permit magnesium vapor to effuse through the silicon under the experimental conditions of approximately 970O to 1220°C and 1 day equilibration time. However, negligible magnesium was lost from the crucible during the quench due to the slow effusion rate through the pores of the graphite. The inner alumina crucible prevented the liquid alloys from contacting the graphite, and the very tightly fitting graphite crucible lids served to retain any magnesium vaporizing from the alloys inside the crucibles during the quenching step.12 The loaded silicon-alumina-graphite cells were positioned, one above another, on a 16-in.-long titanium thermocouple well and tied securely to the titanium tube with thin molybdenum wires held in grooves around the circumference of the graphite crucibles. A thin (0.005-in.) molybdenum strip prevented contact between the graphite crucibles and the titanium. This assembly was lowered into a titanium reaction tube (la in. ID, 16 in. long, $ in. wall thickness) closed on one end which contained a 11/2-in.-long cylinder of magnesium at the bottom. The inner titanium thermocouple well was positioned eccentrically in the large tube because of the eccentric mounting of the cells on the well. Appropriate modifications of the titanium cap"'12 were made to join the inner and outer titanium

Jan 1, 1968

By Allan J. Clark

It is nearly three years since the metallurgy of the Homestake ore was discussed with considerable thoroughness, in a paper1 read before the Institution of .Mining and Metallurgy. Certain changes have been made in this period which are perhaps of sufficient interest to justify a brief description, and it is chiefly with such details and miscellanies that this paper will deal. In the circumstances, a certain amount of repetition is inevitable, but matter treated of in the former paper will be referred to here only when it is necessary for the sake of coherency. For full descriptions of equipment and technique, the former paper should be consulted. The mineralized slates and schists which constitute the ore vary considerably in composition, but the unoxidized ore, perhaps constituting the major part of the reserves, contains either chlorite or hornblende (cummingtonite), with quartz, carbonates of lime, magnesia and iron, and arsenopyrite, pyrite, and pyrrhotite. Ferrous minerals predominate, and this fact has been an important factor in determining the metallurgical treatment. With one or two exceptions the minerals noted are of relatively high specific gravity, and the ore as a whole is exceptionally heavy, many determinations giving an average specific gravity of 3.00. This high specific gravity presents one decided advantage, when the cost of treatment is compared with operations elsewhere, in that the ton, almost universally the basic unit, represents a volume probably less by 10 per cent. than that of many gold ores. On the other hand, this high gravity renders more difficult the discharge of pulp from mortars, its distribution on amalgam tables, and its transportation in launders. In the same way, as attesting the usual balance of such variations of different ores, it may be noted that the needle-like fibers of hornblende (cummingtonite), interlacing throughout the mass, render the ore more difficult to crush than would be anticipated, but on the other hand assist

Jan 1, 1916

By E. S. Bumps, W. F. Craig, M. Baeyertz

Metallurgists have looked at fractures macroscopically for many years and have evolved a vocabulary in which such words as "cleavage," "brittle," "shear," "ductile," "granular," "fibrous," and "silky" are used to describe the appearance of the fractured surface; but the meaning of these words in terms of metal structure is not well established. Observations of the structural meaning of "brittle" and "ductile" fractures in plate steels have been made, notably, by Kramer and coworkers1 and by Tipper.2 Grossman3 has studied the fracture of tempered martensite and combinations of ferrite and martensite. Notwithstanding these and other less concerted attacks on the problem, present understanding of fracture rests more on assumptions and logic than on experiment. It is the purpose of this paper to add a little to the growing fund of experimental observations of the nature of fractures in steel. The particular fractures to be described were obtained in conventional impact testing of an ordinary structural steel shape. In impact tests of the Charpy type, the specimens fail in a characteristic manner that depends on the steel and the temperature of testing. With ordinary structural and many other steel products, an appropriate range of testing temperature will cause a considerable change in the energy absorbed before fracture. This change is known as the energy transition and is accompanied, more or less closely, by alteration in the appearance of the fracture. At testing temperatures below the transition, the terms "brittle," "cleavage," or "granular" are used to describe the fracture; above it, "ductile" or "shear" are often used. Within the transition, the fracture changes from "brittle" to "ductile" by a progression in appearance, wherein the "brittle" portion of the fracture becomes restricted to a smaller and smaller central area of the fracture, as the testing temperature is raised and the "ductile" type of fracture is approached. All this is well known to metallurgists. The specimens under consideration are of the conventional V-notch Charpy type. They were taken from a structural steel shape of the following analysis: C Mn P S Si 0.17 0.46 0.009 0.029 0.03 Both longitudinal and transverse specimens were tested and examined. Fig 1 shows the energy values plotted against testing temperatures in the usual way. The curves for both longitudinal and transverse specimens show an energy transition, although the maximum energy absorbed at testing temperatures above the transition is greater in the case of the longitudinal specimens. Fig 2 illustrates the changes in the macroscopic appearance of the fractures that are associated with the energy transitions shown in Fig 1. Macrographs of the fractured surfaces of the specimens have been identified with the fracture ratings at intervals on each fracture curve. The numerical fracture rating on the ordinate of Fig 2 indicates the percentage of the area of each fracture that was considered to be "brittle" on macroscopic observation. Such rating of the fracture type in impact tests is now customary in many laboratories. Hereafter the specimens will be identified by reference to Fig 2 as 90 pct "brittle," 80 pct "brittle," and so on, in accordance with this macroscopic evaluation of the appearance of the fractured surface. The discussion of the fractures is divided into three parts. The first two are concerned with the mode of fracture and its relation to general structural features. As the same metal-lographic features occur in both longi-

Jan 1, 1950

By M. A. Scheil, S. L. Hoyt

About three years ago eight standard steels were prepared for the cooperative investigation of methods for oxygen analysis, sponsored by the Iron and Steel Division of the American Institute of Mining and Metallurgical Engineers and by the National Bureau of Standards. A preliminary report of the results was made at the annual meeting of the A.I.M.E. in February, 1936. † This report showed the reliability of vacuum-fusion methods and further brought out certain advantages of the fractional vacuum-fusion method. The results obtained by the authors with the latter method will be discussed here, with some comments on the procedure for those who are interested in determinations of gases in steel. Some additional comments are offered on the use of the polarizing microscope for identifying the inclusions in the steel to check and amplify the findings of the fractional vacuum-fusion analysis. For details of the fractional method, see the paper by L. Reeve1. Degassing the Crucible One of the sources of error in vacuum-fusion methods has been the blank gases evolved from the graphite crucible after preliminary out-gassing. We have used 1750" C. as the outgassing temperature. This gives a base pressure at that temperature of less than 0.030 mm. after one hour and of 0.004 mm. on dropping the temperature to 1575" C. At lower extraction temperatures the base pressure is 0.001 mm. at 1050" C., 0.002 mm. at 1170" and 0.003 mm. at 1320' C. Because of the size of our induction coil we are limited to this temperature, although it 'would be advantageous to use 1950" to 2000" C. Hamilton2, after outgassing at 1850" C. for 100 min., was able to reach a base pressure of 0.001 mm. for a temperature of 1700' to 1725" C. This would give a blank corresponding to less than 0.00015 per cent 02 and 0.00005 per cent H2. Chipman and Marshall outgas at 2000" C. for one hour by using a special construction

Jan 1, 1937