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By J. L. Humphrey

The origin of roof bolting is obscure, but is believed to have begun some 40 years ago in the mines of St. Joseph Lead Co. in southern Missouri. It was not until after World War II, and more particularly after 1949, as a result of the concentrated effort of the USBM, that roof bolting attracted widespread interest. It is estimated that at the end of 1954, 26 pct of all bituminous coal mining in the U. S. was being done under roof bolts. Those mines alone use nearly 2,000,000 roof bolts per month, according to USBM statistics. Uses in metal mines are increasing rapidly, as confidence and knowledge grow. The application has found equal success in other fields, such as tunneling work for dam and waterway construction and right of way maintenance on highways and railroads.

May 1, 1956

By W. W. Norton

The gradually increasing proportion of sulphide ores which lead smelters of to-day are called upon to handle has caused the roasting problem to become one of ever greater importance. Mines have increased in depth, methods of concentration have improved, competition in the purchase of ores has become more keen and it has been clear that new and modern methods of eliminating sulphur must receive a large share of attention. We may look back a score of years or so and recall the old hand roasters, some of which turned out a finely divided roasted product, and others fashioned with a "fuse-box" wherein the roasted ore was slagged. Then came mechanical furnaces of several types, the Bruckner cylinder, the Brown-O'Harra, the Ropp, and others, all designed to cut out the cumbersome hand labor of the old reverberatories. Roasting costs were thereupon reduced and tonnages stimulated to a gratifying extent. However, it seems to have been early recognized that this very feature of a greater amount of roasted sulphide ore as compared with oxide ore brought with it a train of difficulties at the blast furnaces. The mechanically roasted ore was fine physically, the blast furnaces were choked and the troubles of the smelterman were not at an end. Then the Huntington-Heberlein pot system of roasting appeared upon the scene, and later on the Dwight-Lloyd machines were invented, and inasmuch as both of these processes were designed not only to roast the ore but to agglomerate it as well, it was apparent that distinct steps in advance had been achieved. At the Murray plant, modern up-to-date roasting practice is fully exemplified and there are now in successful operation roasting furnaces or devices of several sorts: namely, Godfrey revolving-hearth furnaces, Wedge multiple-hearth mechanical roasters, Dwight-Lloyd sintering machines, and Huntington-Heberlein pots. Godfrey and Wedge furnaces will properly handle material high in sulphur, say ores with 25, 30, and 35 per cent. of that element; D. & L. machines and H. & H. pots will positively not treat efficiently ores or mixtures containing anywhere near the sulphur content mentioned, but are confined to charges containing in the neighborhood of 15 or 18 per cent. In passing, it may also be explained that, so far as the knowledge of the writer goes, Godfrey and Wedge furnaces do not economically eliminate sulphur to an extent

Jan 1, 1915

Abbey, Robert Graham, District Mgr. The W W. Sly Mfg. Co,. 50 Church St, New York, N. Y. '21 Abbott, A. N., Mines Supt., Mazapil Copper Co., Ltd ..Concepcion del Oro, Zac., Mexico. '23 Abbott, Argyle Campbell, Dev. Dept, E I du Pont de Nemours & Co, Wilmington, Del. '29 Abbott, Clarence E., V.P, Charge of Raw Materials, Tenn. Coal, Iron & R. R. Co, 1242 Brown-Marx Bldg, Birmingham, Ala. '04 Abbott, Louis Benjamin, Chief Engr., Elkhorn Div., Consolidation Coal Co, Jenkins, Ky. '15 Abeel, George H., Jr., Cons. Min. Engr Box 427, Santa Monica, Cal. '18 Abel, Albert E., Asst. to Pres, Valley Mould & Iron Corp Hubbard, Ohio. '19 Abel, Raymond L., Asst. Prof., Dept. of Pet Refin., Univ. of Pittsburgh Pittsburgh, Pa. '28 Abell, Leo M., Research Engr, Sullivan Concentrator Chapman Camp, B. C., Canada. '31 Abernathy, George Elmer, Prof. of Geol. & Min . Kansas State Teachers College, Pittsburg, Kans. '20 Aborn, Robert H., Research Lab, U. S. Steel Corp. Lincoln Highway, Kearny, N. J. '19 Abozeid, Mahmood, Dept. of Mines & Quarries Cairo, Egypt. '26 Abraham, Arthur W. Box 1466, Bakersfield, Cal. '20

Jan 1, 1923

By AIME AIME

The XCVIIth meeting of the Institute for the reading and discussion of papers will be held at Spokane, Wash., beginning Monday, Sept. 27, 1909, as already announced in Special Circulars of May 8 and Aug. 14, 1909, and in the Bulletins for June, July, and August. The meeting will be preceded by a tour through Yellow stone Park and visits to Butte and Anaconda, and will be followed by visits to the Coeur d'Alene district, to the Alaska-Yukon-Pacific Exposition at Seattle, to the mining- and smelting-plants near Salt Lake, and to the iron- and lead- and zinc-plants at Pueblo. The special train for the party' will leave Chicago, September 16, and return about October 12. Details of the itinerary are given later in this announcement. The Secretary of the Spokane Local Committee is Lyndon K. Armstrong, 615 Hyde Block, Spokane, Wash., to whom should be addressed all inquiries concerning local matters. The control of the papers and proceedings will remain in charge of the Institute office, as usual. It is greatly to be desired, both in behalf of the Institute and in recognition of the many courtesies to be extended on the trip, that the excursion party be made larger. Exceptional facilities to visit the many mines and smelters have been freely provided; and members are requested to make all reasonable effort to attend the meeting at Spokane and participate in the excursions. For those who cannot join in the entire trip, it may be possible to provide special Pullman accommodations after leaving Yellowstone Park. In order to make the necessary arrangement, however, the names of members and guests contemplating this partial trip should be sent at once to Theodore Dwight, 29 West 39th Street, New York City. The general cost of the trip per member will be $300, which includes transportation, berth, and meals for the entire trip from

Sep 1, 1909

By E. J. Pasierb, H. W. Paxton

Mavkers ill a diffusion couple in the iron-chromium system move towards the high chromium side indicating Dcr > DFe at the marker composition. By a combituztion of measurements of D& and D a: a function of composition, this is also shown independently. DFe is calculated as a function of composition. and shown to be in reasonable agreement with measured values by other workers. MEASUREMENTS of marker movements in diffusion couples have been used from time to time to demonstrate that a vacancy or interstitial mechanism may be operative. Since there is a possibility that ring diffusion1 may be operative in chromium, the present experiments are of interest in showing some non-ring mechanism in iron-chromium alloys around the equiatomic composition. EXPERIMENTAL PROCEDURE The movement of markers originally at the interface between 1-in. sq sections of pure Cr (6 mm thick) and outer slabs of 30 Cr-70 Fe alloy was followed as a function of time at temperatures from 1150" to 1425"C, in a Kanthal-wound furnace. Temperature control was +5°C over extended periods. The analyses of these alloys are given in Table I. Selection of suitable markers presented a considerable experimental problem; the eventual solution was to draw quartz rod down to 0.01 cm and seat this in V-grooves 0.01 cm deep on each side of the chromium prior to welding. A preliminary experiment in which the groove was machined in the alloy gave identical results. Welding was accomplished by passing a heavy current through specimens under moderate pressure in a helium atmosphere. This method produced good welds with a planar interface as shown by subsequent metallo-graphic investigation. Any markers which did not adequately fill their groove and showed subsequent contamination from the atmosphere during heat treatment were not considered reliable. The composite sample was ground and metal-lographically polished on the four sides perpendicular to the interface. Fiducial marks (deep milled slots) were made outside the diffusion zone to check on total volume change. All necessary measurements were made on a metallograph reading to +0.0005 cm. The samples were wrapped in tantalum foil and given diffusion anneals for times to 200 hr in carefully purified dry hydrogen in a sealed McDanel porcelain tube. Chromium-zirconium chips were introduced near the specimen as an additional getter. The specimens were cooled relatively slowly after the diffusion anneal to preserve the McDanel tube but no significant error in effective time at temperature was thereby introduced. At least 1 mm was ground off the surface before measurements were taken. It was observed that the grain size following short diffusion anneals was several mm and was appreciably larger in the 30 Cr alloy than in the pure Cr. No significant grain boundary penetration was present as indicated by the etch limit. The results are presented in the next section. Measurements of D were made by standard sectioning techniques with chemical analysis. Machining difficulties limited the

Jan 1, 1961

By E. B. Spice

Although much may be learned about the economics of cold weather operations by studying successful mining ventures in southern and central Canada, it is the purpose of this article to extend the study by considering only permafrost areas. Geographically this means most of the country north of the 60th parallel. In this area, at the present time, only five Canadian companies are carrying on routine and successful mining operations on a year-round basis. However, there have been some score of unsuccessful ventures, and a number of properties in the development stage show promise of being producers. Problems of cold weather are worthy of study. It may be pointed out that successful mines in this area face problems of isolation and costly transportation as well as cold weather. To reach valid conclusions, consider the development of a mythical mineral deposit located on the 65th parallel in the heart of the barren lands; problems of isolation and transportation will be ignored.

Jul 1, 1956

By Noel Jarrett, Allen S. Russell, Bernard M. Starner, Stanley C. Jacobs

A process has been developed to refine high-grade commercial aluminum to 99.99 pct purity. This enzploys precipitating titanium, vanadium, and zirconiu~ as borides. The upgraded liquid is partially crystallized under conditions that prevent massive freezing. The resulting crystals are compacted and washed free of adhernig impure liquid aluminum by melting the top crystals while draining off the liquid. Finally, the bottorn portion of the crystal bed is melted and removed as the pure product. Leakage from the crystallizat~on vessel is prevented by a layer of alumina granules that are not wetted by the aluminum. ALUMINUM of 99.99 pct purity is desired in a variety of applications. These include electrolytic capacitors, catalyst carriers, decorative trim for automobiles, aluminum powder, and high-strength alloys. This market was for many years filled by refining commercial-purity aluminum in a three-liquid-layer electrolytic cell of the type originally proposed by Hoopes. To meet the expanding need for lower-cost high-purity aluminum, a refining process based on chemical precipitation and fractional crystallization was developed. The availability of this super-purity metal was announced in November 1961, and three patents1-3 relating to the process were issued in 1965. An alternate process, comprising continuous fractional crystallization of a portion of a liquid-aluminum feed stream under conditions of strong agitation at the surface of the growing crystals, was published by Dewey4 in 1965. Earlier proposals by Larsen 5 and by Regner6 also emphasized the advantage of rapid agitation of the melt in the region of the crystallization zone. johnson 7 more recently proposed extracting purified aluminum from an alloy by mixing crystals of pure aluminum into the molten alloy, allowing them to grow, and removing the pure aluminum as by casting. Aamot's 8 recent patent describes a freeze refining process that involves controlled partial freezing against cooled moving retort walls. The Alcoa process to produce high-purity aluminum is schematically described in Fig. 1. Relatively pure aluminum is treated with boron in a furnace (a) to precipitate high melting point impurities, the supernatant liquid is transferred to a crystallization vessel (b), the liquid is partially crystallized with mechanized "tamping" (c), the remaining impure liquid is tapped out and the crystal bed partially and directionally re-melted to wash the underlying crystals (d), and the balance of the crystals is melted and withdrawn as high-purity aluminum (e). PRINCIPLES OF FRACTIONAL CRYSTALLIZATION Commonly encountered impurity elements form two types of systems with aluminum. Titanium, vanadium, and some other transition elements in periodic groups IV, V, and VI are the high melting point impurities. Initial solidification of aluminum containing small percentages of these elements will produce solid markedly enriched in them at temperatures slightly above the freezing point of high-purity aluminum. Most other elements, such as silicon and iron, produce eutectic type reactions with aluminum. In this case the first solid formed on initial solidification at temperatures slightly below the freezing point for high-purity aluminum is markedly depleted while the remaining liquid is enriched in these elements. The equilibrium change in composition during solidification of aluminum contaminated with silicon, iron, or titanium is illustrated in Fig. 2. Here, for clarity, the temperature scale is expanded beyond the

Jan 1, 1968

By J. C. Uy, T. E. Davidson, A. P. Lee

The effects of hydrostatic pressures to 26 kbars on the micro structure of poly crystalline Cd, Zn, Bi, Sn, Zr, Mg, Cu, and Fe were examined. Pressure-induced microscopic plastic flow in the form of boundary migration, slip, multiple slip, or twinning has been observed either singly or in combination in cadmium, zinc, bismuth, and tin. No deformation was observed in zirconium, magnesium, copper, and iron. The occurrence of such deformation, in terms of its intensity and initiation pressure, relates directly to the degree of anisotropy in the linear compressibility. Pressure cycling does not significantly affect the residual tensile properties of a zinc alloy which exhibits pressure-induced deformation similar to that of Pure zinc. CLASSICAL elastic theory predicts that a superim-posed hydrostatic pressure will not induce shear stresses in an ideal material. Thus, in the case of homogeneous and isotropic materials plastic flow will not occur as a result of pressure exposure, regardless of the magnitude of the pressure, unless some form of phase transformation or permanent density change takes place. However, real materials, such as metals, often vary considerably from the condition of homogeneity and isotropy. For this reason, Vu and johannin' examined and observed hydrostatic pressure-induced microscopic deformation in polycrystalline cadmium and, zinc, but not in aluminum, to pressures of 9 kbars and indicated that its occurrence is related to anisotropy in the linear compressibility. In addition, Davidson and omaan' have reported pressure-induced deformation in polycrystalline bismuth below the 1-11 transformation pressure. It becomes apparent then that under certain conditions hydrostatic pressure can induce localized internal shear stresses in some metals of sufficient magnitude to cause plastic flow. In this work, eight pure single-phase metals of different lattice structures and degrees of elastic anisotropy were examined after pressure exposures of up to 26 kbars in order to establish the conditions under which such deformation occurs and the type of deformation as a function of pressure. The effects of pressure cycling on the mechanical proper-

Jan 1, 1965

By O. W. Simmons, L. W. Eastwood, C. M. Craighead

The results of a preliminary study of 113 ternary titanium-base alloys are described. The compositions investigated were as follows: 1. Ternary titanium-carbon alloys containing copper, silicon, vanadium, chromium, manganese, iron, or cobalt. 2. Ternary titanium-nitrogen alloys containing chromium. 3. Ternary titanium-chromium alloys containing additions of vanadium, molybdenum, tungsten, cobalt, or nickel. 4. Ternary titanium-manganese alloys containing additions of silicon, chromium, tungsten, or iron. Tensile properties, minimum bend radii, hardnesses, response to heat treatment and aging treatment, and phase relationships for these alloys were determined. THIS is the second in a series of papers describing some of the results of the exploratory work on titanium alloys being conducted at Battelle Memorial Institute for the Wright-Patterson Air Force Base. The work with the binary alloy systems has been described in a previous publication.' This paper describes ternary titanium-base alloys as follows: 1. Ternary titanium-carbon alloys containing copper, silicon, vanadium, chromium, manganese, iron, or cobalt. 2. Ternary titanium-nitrogen alloys containing chromium. 3. Ternary titanium-chromium alloys containing additions of vanadium, molybdenum, tungsten, cobalt, or nickel. 4. Ternary titanium-manganese alloys containing additions of silicon, chromium, tungsten, or iron. As the preparation and fabrication of the 0.5-Ib experimental titanium alloy ingots to 14-ga sheet, as well as the methods of testing used in this work, have been described in the first paper of this series, Titanium Binary Alloys, no further discussion of these techniques will be given. Ternary Alloys Containing Carbon The following alloys of titanium, containing carbon and one other metal, were investigated: 1. 0.25 pct carbon; 1, 2.5, and 5 pct copper. 2. 0.25 pct carbon; 1, 2, and 3 pct silicon. 3. 0.25 pct carbon; 1, 2.5, and 5 pct vanadium. 4. 0.25 pct carbon; 2.5, 3.5, 5, 10, and 15 pct chromium. 5. 0.5 pct carbon; 2.5, 3.5, and 5 pct chromium. 6. 0.25 pct carbon; 1, 1.75, 2.5, 3.5, 5, 7.5, and 10 pct manganese. 7. 0.5 pct carbon; 1.75, 2.5, 3.5, 5, 7.5, and 10 pct manganese. 8. 0.25 pct carbon; 0.25, 0.5, 1, and 2 pct iron. 9. 0.25 pct carbon; 1, 2, and 3 pct cobalt.

Jan 1, 1951

By Joseph T. Singwald

INTRODUCTION THE purpose of this chapter is to present the diagnostic features (geologic, mineralogic, chemical, and physical) of the principal types of hypogene ore deposits recognized in current genetic classifications, and to classify the ore deposits of the western United States into those types. The genetic divisions used and the criteria determining them are essentially those followed by Lindgren in his Mineral Deposits. Deviations from Lindgren represent either changed conceptions since 1928 (the date of the third edition of Mineral Deposits) due to advance in knowledge or the inevitable differences of opinion between experts in active fields of investigation. Though nineteen economic geologists have been given free hand in presenting their particular topics, there are no fundamental departures in the chapter from the principles set forth by Lindgren. It would be entirely beyond the capacity of a single chapter to give a comprehensive geologic description of all the ore deposits of the western United States. Descriptions of individual deposits have been restricted to those features that are of most diagnostic genetic value. All of the more important deposits receive that much attention. Deposits of lesser economic importance and those inadequately known geologically are treated more briefly or merely cited under what seems to be their proper genetic assignment. The geographic limits of the descriptive matter are the Black Hills and the United States between the Rocky Mountains and the pacific Coast. Capacity of the chapter has made it necessary to impose these geographic limits.

Jan 1, 1933

By L. L. Wyman

SINCE the observations of Heyn,1 relative to the embrittlement of copper after having been heated in hydrogen, this subject has received considerable attention from later investigators. The published works of Archbutt2 and of Bengough and Hill3 give the reasons for this embrittlement-the formation of steam by the reaction between cuprous oxide and hydrogen. From Ruder,4 Pilling,5 Moore and Beckinsdale,6 Bassett and Bradley,7 and from Smith8 can be obtained quantitative data concerning the action of hydrogen and other reducing gases on copper samples having various oxygen contents. This problem has been discussed from a practical standpoint by Fuller9 who calls attention to some of the instances of this embrittlement encountered in the manufacturing field. The examples he cites may be considered typical cases of copper embrittlement which were incident to the process of manufacture. In many cases, such difficulties are overcome by changes in the manufacturing process.

Jan 1, 1931

By L. K. Jetter, C. J. McHargue

The use of axis charts for representing the texture of cold-rolled thorium sheet was compared with conventional pole figures. Four texture components were deduced from the axis charts and shown to be consistent with the pole figures. It was shown that consideration of the pole figures alone could lead to an apparent component which is the average of two actually present. It was also shown that the spread about the "ideal" textures and the amount of material associated with each could be readily obtained Fom the axis chart method. BECAUSE of the crystallographic nature of the deformation mechanisms in metals, plastic flow results in the alignment of certain crystallographic directions with the primary flow directions. In the study of the "preferred orientation" thus developed, one wishes to discern the distribution of the crystallographic directions with respect to some reference direction, usually a direction related to the fabrication procedure, such as the rolling direction. The pole-figure method, introduced by ever,' involves the plotting of the distribution of the poles of some family of planes on a stereographic projection which places the reference direction(s) at the north pole and/or in the center. By noting the angles between the reference directions and concentrations of poles on several such pole figures, one can deduce the crystallographic directions which are aligned with the reference directions. If the preferred orientation is relatively simple and well-developed, one to three pole figures may be sufficient for obtaining the desired information; if there are several texture components, more pole figures may be needed. A significant improvement in the method of representing the textures in wires and rods resulted from the introduction of the "inverse pole figure" or axis-distribution chart by Harris.2 Such a chart gives directly the distribution of the reference axis relative to the standard stereographic projection. There has been widespread acceptance of this method for the representation of fiber textures, and methods have been proposed for converting observed diffraction intensities into axis densities.2-6 The suggestion by Mitchell and Rowland3 and Jetter, McHargue, and williams5 that sheet textures could be represented as distributions of rolling, normal, and transverse directions have been criticized on the basis that they offer no significant advantage over a combination of two ordinary pole figures and that it has not been proved that sheet textures can be treated as quasi fiber textures.6 If the purpose of a texture determination is to study some property which is related to the orientation of a particular crystallographic plane or direction, then conventional pole figures certainly are sufficient. For example, the distribution of the slip planes in face-centered cubic metals (the (111) pole figure) serves to indicate the variation in mechanical properties of sheet. On the other hand if the study is directed at an understanding of the factors influencing texture formation, it is desirable to know not only the preferred orientation but the kind and degree of spread from it and the relative amounts of material in each component, if there are more than one. Axis charts give this information as well as the orientation distributions. Consider the procedure for deducing a texture component from a pole figure for the (111) planes

Jan 1, 1961

INTRODUCTION Trade financing is a particularly important component of short-term financing for a minerals company since errors, extra costs, or payment delays/defaults can easily wipe out the profit margin on a particular shipment or can cause problems when arranging purchases of e.g. reagents. It is required to make any minerals operation function and does not have to be cross-border to require proper management. Sources of working capital are as follows: 1. Extended credit terms from suppliers 2. Inventory loans from banks, finance companies 3. Accounts receivable financing or factoring 4. Credit lines or overdraft facilities from banks. TRADE CREDITS These are provided under the familiar terms "net 10 days" or payment due by the "10th day of the following month." Thirty days for payment is usual but longer periods can be negotiated with regular suppliers. Shipment may be made on open account with specified periods for settlement. In the mining industry, a custom smelter gains trade credit by paying for concentrates three months after the month of shipment. INVENTORY LOANS Various forms of inventory finance are provided via "floor-plan" or warehouse financing. A set percentage, usually 60%-80%, of a good-quality, readily saleable inventory item (e.g. bullion, concentrates, ingots) will be provided by a bank or finance company which will usually have security over these products and has a right to inspect the goods from time to time. Legal security will he achieved by warehouse receipts, floating liens, chattel mortgages, trust receipts, or through collateral management service companies. The latter certify control over stock or distribution outlets and often carry insurance against fraud. Costs range around 1.5% - 2.0% p.a. or more plus some fees to cover out-of-pockets or other costs. ACCOUNTS RECEIVABLES Accounts receivable financing is based on the company's generation of satisfactory receivables which are continuously assigned to a bank or finance company ("factoring"). Because of the risks in being able to collect receivables, such as payments to a smelter for its blister copper shipments to a refinery, this form of financing costs as much as 3% - 5% of the debt amount purchased plus an additional charge for processing paperwork. Receivables can be purchased with or without recourse and on a notification or non-notification basis to the client's customer to, respectively, pay the invoice directly to the bank or not. LETTERS OF CREDIT Letters of Credit ("L/C's") are a common feature of international trade finance whereby a bank, at the request of the buyer, issues a written undertaking to an exporter to pay a specified sum of money within a set time on presentation of previously specified documents. This undertaking means that the exporter is no longer relying on the credit standing and integrity of the foreign importer. A dispute about shipment does not otherwise affect the obligation to pay upon presentation of a "clean" set of documents. These documents include the hill of lading and other documentation, often on standard "form" bases. There are a number of conventions and techniques in L/C's such as irrevocable/revocable L/C's, time L/C's, confirmation/advising L/C's and transferable L/C's. These are tools to adjust for the varying risks that the importer will not pay. Other routes where one is comfortable with an importer include documentary sight hills (D/P hill), documentary term bills (D/A bill), and, of course, open account.

Jan 1, 1985

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

By C. N. J. Wagner, E. N. Aqua

Dilute Fe-Si alloys (0 to 5 wt pet Si) were cold-worked by making filings at room temperatuve. The analysis of the broadening of the X-vay powdev pattern peaks yields anisotropic particle sizes normal to the (110), (100), and (112) planes which are a consequence of deformation faults (probability a) and twin faults (probability p). The combined fault probability (1.5a +ß) increases from 0.01 in pure iron to 0.02 in Fe-5 pct Si. The root mean square stvains vary with crystallographic ovientation due to elastic anisotropy of the alloys, and increase from about 0.0035 in pure iron to 0.005 in Fe-5 pct Si measured in the [100] direction. Assuming that deformation and twin faults occur with equal probability, the X-ray data would imply that the stacking-fault energy does not change upon alloying. THE crystallographic aspects of the plastic deformation of dilute Fe-Si alloys has been studied many times since the observation of glide band structures by Barrett et a1.l These glide bands were much straighter than the wavy bands observed by Gough2 in unalloyed iron nearly 40 years ago. This difference in the morphology of the slip band structure has been verified many times, most recently by replication electron microscopy3 and dislocation etch-pitting methods.4,5 These observed differences in deformation behavior have been considered to result from the degree of cross slip that occurs in pure iron and in the Si-Fe alloys. The lowered tendency for cross slip would result from a lowering of the stacking-fault energy of iron by the silicon alloying addition. Experimental evidence for this lowered stacking-fault energy in the Si-Fe alloys, obtained with transmission electron microscopy, is the observation of dissociated dislocations in Fe-6 pct si6 and Fe-3 pct Si alloys,7 and the observation of sharply defined cellular substructures in Fe-3 pct si6,7 compared to the more diffuse substructure in zone-refined iron.' The activation energy for recovery of cold work is greater in the Si-Fe alloys than it is in pure iron, indicating that cross slip has become a more difficult process.9 The purpose of this investigation is to determine the change in stacking-fault probability from the broadening of powder pattern peaks in dilute silicon-in-iron solid solutions, when cold-worked at room temperature. The knowledge of the stacking-fault probability and the dislocation density, both of which can be deduced from line-broadening analysis of two orders of reflections from (110), (200), and (112) planes, will permit us to calculate the change in stacking-fault energy upon alloying silicon into iron. Previous X-ray investigation of cold-rolled Fe-5 wt pct Si (100)[001 ] single crystals did not reveal any line broadening, whereas cold-rolled Fe-3.1 wt pct Si (001) [110] and (001)[100] single crystals10 showed line bro2dening as a consequence of small particle sizes (-200A) and root mean square strains (-0.25 pct), which are comparable to those found in cold-worked iron filings.11 EXPERIMENTAL PROCEDURE A series of five Fe-Si alloys containing nominally 1 to 5 wt pct Si and pure iron were cold-worked by making filings at room temperature. The actual silicon content deviated at the most by +0.1 pct which is of no significance in the present study. The carbon contents of these materials were less than 0.02 pct. The X-ray diffraction patterns were measured with molybdenum, cobalt, and iron radiation using a GE and a Philips diffractometer. The (110)-(220), (200)-(400), and (112)-(224) pairs of reflections were

Jan 1, 1968

By C. E. Birchenall, R. H. Condit, M. J. Brabers

In the oxidation of pure iron above 700°C the overall rate is determined mainly by the rapid growth of wiistite, through which iron ions can diffuse rapidly.' Nickel added to the iron progressively decreases the stable range of composition of wustite.' When enough nickel is added to eliminate wiistite as a stable phase, the spinel is the fast growing phase. This investigation was undertaken to test the hypothesis that nickel substituting for iron in magnetite might decrease the rate of spinel growth by reducing the iron mobility. Nickel ferrite boules grown by the flame fusion process were purchased from the Linde Co. Chemical analysis gave an atomic ratio of iron to nickel of 2.88 and showed no other cations. They were cut into discs and ground to give flat, parallel faces. The experimental procedure employed was like that of Eisen and Birchenall in which the distribution of radioactivity diffused in from a vapor deposited surface layer was determined by counting the residual activity through a series of ground faces. The diffusivities were calculated in a manner consistent with the requirements discussed by Condit and BirchenallP The details will be given in connection with a more extensive spinel diffusion study now in progress. The results of the measurements are shown in the figure in comparison with earlier data on magnetite1 and zinc ferrite. The uncertainties arising from scatter in the activity vs distance relationship and uncertainties in the temperatures are shown by flags. Despite the scatter it is clear that substitution of a considerable part of the iron in magnetite by nickel, in this case about one third decreases the iron mobility substantially. sachs' determination of the distribution of iron and nickel in scales on iron-nickel alloys appears to show that nickel is less mobile than iron in the spinel layer. It is evident, therefore, that nickel plays several roles in reducing the oxidation rate of iron-nickel alloys. 1) It reduces progressively the stability range of wiistite. ' 2) It reduces progressively the stability range of the iron-nickel spinel phase in terms of the variation in cation to anion ratio.' 3) As shown in this investigation, it reduces the cation mobility in the spinel phase which is the faster growing phase in the absence of wiistite. The fe was obtained from the Oak Ridge National Laboratory. The research was supported by the Air Force Office of Scientific Research (ARDC) under contract number AF 18(600)-967.

Jan 1, 1961

By John J. Croston

IN the closing months of 1936 the copper industry gave every evidence that it was at last on the threshold of an improved era. At the beginning of the year prices stood at 9 ¼ ¢, which in itself was a great improvement over prices prevailing for the three previous years. Industry generally was showing signs of moving forward in this country, and business was definitely good in certain foreign quarters. The threat of war and preparations for rearmament in Europe and Asia acted as a further stimulus to purchasing. By midsummer the situation had so improved and stocks had been so reduced that the cartel of foreign producers (including American producers with foreign mines) decided to increase the production quota to 75 per cent on Aug. 1. Large-scale buying gave continued strength to the price and by Oct. 1 the quota was increased to 80 per cent, and again on Oct. 15, to 85 per cent. Notwithstanding this the price of copper continued its advance and on Nov. 1, with stocks declining continuously, the cartel increased operations to 95 per cent, then to 105 per cent on Nov. 5. In the meantime the domestic producers, because of the great increase in home consumption, had increased their production by nearly one-half. At the close of the year copper sold at 12¢ per pound, and since the turn of the present year has reached 17¢. This rapid increase has not been wholly justified. Much of the increase was due to the legitimate demands of recovering industry, but rearmament orders plus accumulation of reserve stocks in case of war, purchases in anticipation of labor strikes and purely speculative activities on the London Metal Exchange accounted for the balance. Certainly in view of the state of industry and the general world price level, it appears unnecessarily high. Talk of a copper shortage is sheer nonsense, the recent condition in the market being created by overbuying, leaving but a small volume for speculative supplies. It takes some months for an increase in mine output to reach the market, but production is again overtaking apparent consumption, stocks have begun to increase, and this, together with the reopening of many small

Jan 1, 1937

By J. A. Berger, G. W. Wiener

Several transition metal nitrides have been prepared and their saturation magnetization determined. On the basis of an atomic model of ferromagnetism involving a consideration of nearest neighbor interactions and the assumption that all atomic moments of the metal point in the same direction, it appears that the nitrogen interacts with d-shell of the transition metal in such a way as to reduce the magnetic moment. THERE is a large class of materials having metallic properties which are formed by a combination of hydrogen, boron, carbon, oxygen, or nitrogen with the transition metals. Several attempts have been made to establish the type of metal-nonmetal bonding in these interstitial alloys because it is believed that many of the physical properties of these materials are determined by the characteristics of this bond. Several of these alloys are ferromagnetic, and thus a powerful method is available for investigating the structures in a direct manner by measuring the saturation magnetization. The latter is a fundamental property of ferromagnetic metals and alloys which depends primarily on the electron distribution surrounding the atom. For the first row of transition metals, this refers specifically to the 3 d-shell. Since bonding involves the electronic configuration between atoms, there is reason to suppose that a relationship exists between ferromagnetism and bond type. In the case of the interstitial structures studied in this work, bonding will refer to the distribution of electrons between the transition metal and the nonmetal. Since these alloys have metallic properties, it is further proposed that any bonding interactions will involve the outer p-shell of the interstitial element and the incomplete d-shell of the transition metal. If this is the case, then the relationship between ferromagnetism and metal-non-metal bonding is established qualitatively. In order to investigate the subject quantitatively, certain transition metal nitrides were chosen because they have simple crystal structures, are ordered alloys, and are ferromagnetic. They also have sufficiently high saturation magnetization to be of technical interest. Currently there are two major theories of ferromagnetism, each of which has been applied to the interpretation of the saturation magnetization in terms of atomic structure. They are usually referred to as the band theory and the atomic theory. The former has found widespread application to the study of pure metals and certain solid-solution allays. However, it has not been applied to the interstitial structures or ordered alloys because it does not interpret the properties directly in terms of the crystal structure. The atomic theory on the other hand is especially suited to the study of interstitial structures because it permits an interpretation of ferromagnetic phenomena in terms of the crystal geometry. As has been pointed out previously, the nitrides have simple ordered crystal structures and, therefore, the choice of the atomic theory for the interpretation of the data is a natural one. One of the prime difficulties with the atomistic theory is that its mathematical justification is much more difficult, and for this reason its general acceptance will depend to a large extent on the value it has in explaining and predicting the results of experiment. Before the presentation of the theoretical basis for understanding the metal-nonmetal bond, it is useful to review the ideas existing prior to this work. Four different interpretations have been given to the metal-nonmetal bond. These are summarized as follows: 1—acceptance of electrons by the nonmetal from the incomplete d-shell of the transition metal, 2—transfer of electrons from the nonmetal to the incomplete shell of the transition metal, 3—no exchange of electrons between the two atoms, and 4— a resonating type of bond involving the p electrons of the interstitial atom giving rise to half bonds. Zener'-4 in a recent series of papers has proposed a new theory of ferromagnetism and has developed an explanation of the observed saturation magnetization of iron nitride (Fe,N) using the concept that nitrogen accepts electrons from the 3d-shell of iron. Jack," on the basis of atom size considerations in iron carbonitrides, has proposed that nitrogen transfers or donates electrons to the inner 3d-shell. He found that the effective size of the carbon atom was less than that of nitrogen and thus suggested that the interstitial atoms give up electrons. Kiessling" has studied the borides of several transition metal atoms and proposed that boron loses one p electron to the transition metal. He postulated that the additional electron added to the metal lattice compensates for the loss in metallic properties which results from the increased metal-metal atom separation. GuillaudT3" has proposed similar arguments from some recent magnetic studies he had made on manganese nitride. However, he did not base his conclusions on a quantitative argument. Pauling," in a recent paper, discussed electron transfer in in-termetallic compounds. He classified nitrogen as a hyperelectronic atom which can increase its valence by giving up electrons. He classified the transition metals as buffer atoms which are capable of either accepting or giving UP an electron. He pointed out that two factors are operating which promote electron transfer because they lead to increased stability. The first is an increase in the number of bonds, and the second is a decrease in the electric charges on the atoms. These ideas when applied to the interstitial nitrides would indicate a viewpoint favoring electron transfer by nitrogen to the transition metal. Hagg7s arguments in favor of no exchange are adequately summarized by Wells." Implicitly, Hagg

Jan 1, 1956

By John J. Croston

In the closing months of 1936 the copper industry gave every evidence that it was at last on the threshold of an improved era. At the beginning of the year prices stood at 91/4c, which in itself was a great improvement over prices prevailing for the three previous years. Industry generally was showing signs of moving forward in this country, and business was definitely good in certain foreign quarters. The threat of war and preparations for rearmament in Europe and Asia acted as a further stimulus to purchasing. By midsummer the situation had so improved and stocks had been so reduced that the cartel of foreign producers (including American producers with foreign mines) decided to increase the production quota to 75 per cent on Aug. 1. Large-scale buying gave continued strength to the price and by Oct. 1 the quota was increased to 80 per cent, and again on Oct. 15, to 85 per cent. Notwithstanding this the price of copper continued its advance and on Nov. 1, with stocks declining continuously, the cartel increased operations to 95 per cent, then to 105 per cent on Nov. 5. In the meantime the domestic producers, because of the great increase in home consumption, had increased their production by nearly one-half. At the close of the year copper sold at 126 per pound, and since the turn of the present year has reached 17c. This rapid increase has not been wholly justified. Much of the increase was due to the legitimate demands of recovering industry, but rearmament orders plus accumulation of reserve stocks in case of war, purchases in anticipation of labor strikes and purely speculative activities on the London Metal Exchange accounted for the balance. Certainly in view of the state of industry and the general world price level, it appears unnecessarily high. Talk of a copper shortage is sheer nonsense, the recent condition in the market being created by overbuying, leaving but a small volume for speculative supplies. It takes some months for an increase in mine output to reach the market, but production is again overtaking apparent consumption, stocks have begun to increase, and this, together with the reopening of many small

Jan 1, 1937

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally.' Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan,3 show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used' for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan's pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision; using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by, the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.5 However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,' has been deduced for these frequencies: [3fB = 9.20•'./V•Vn- (n-1) • (n+2) /8[1]] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts' as the order of the harmonic. As an example, Spedden and Hannan's published motion picture of, a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsymmetric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat I than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system, of one degree of freedom can be applied: [1E/m[2] fP = 27] Here f, is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: [t~ = 2/f = 7r\/m/E[3]] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson' 1831) [aP = 4 D2.pL•g•h +7rD•y sin a[4]] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, pL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of-the liquid in cm, y the surface tension in dynes per cm and a the supporting angle' or the one required to insure equilibrium, a being smaller than the contact angle ?. Although demonstrated by Poisson, it has not

Jan 1, 1952