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By C. R. Austin

Tan investigation described in this paper deals with the development of high-temperature alloys of the Konel series over a considerable period of time at the Research Laboratories of the Westinghouse Electric and Manufacturing Co. The word "Konel" has been coined to designate a class of alloys which are essentially nickel-cobalt-iron with other elements added, usually in small quantities. Most of these alloys contain titanium, usually about 2.5 per cent. The main consideration related to strength at high temperatures but the thermionic characteristics of the alloys was also of considerable importance. It is, however, with the mechanical properties at elevated temperatures that we are herein concerned. Much attention has also been devoted to their age-hardening characteristics. There is little need to stress the utilitarian aspect of this subject, as it has been discussed frequently. Alloys exhibiting superior properties at normal or elevated temperatures rapidly find many suitable applications. There may be some question, however, as to what constitutes a "superior alloy, " or an alloy that may have good service possibilities at high temperatures. The problem is complex and various means have been employed to predict the useful life that may be expected of a material. In recent years the "creep limit" has been used as the best means of evaluation. Such tests necessarily are prolonged and hence collection of data is very slow. In a general survey of many alloys therefore the creep test is not desirable and recourse must be had to much shorter time tests in order more rapidly to select alloys which appear to show promise. For this reason the present survey has been made using the high-temperature tensile test and a bend test developed by Howard Scott.1 In the tensile test the conditions have been standardized for all tests, so that values obtained are at least comparable, one alloy with another, although the absolute values recorded merely indicate the mechanical properties at the given temperature under a definite rate of loading.

Jan 1, 1931

By John Chipman, Theodore B. Winkler

IN order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chipman,3 dealt with the simplest possible slag system that would resemble those found in the basic open hearth-the slag system consisting of CaO-MgO-SiO2-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemistry of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, Si02, FeO, Fe203, P205, MnO, A1203 and CaF2, but not all of the slag samples contained all of these components at one time. REVIEW OF LITERATURE Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Brings4' von Samson-Himmelstjerna,5 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution ratios

Jan 1, 1946

By W. W. Anderson, D. G. Girton

The photoluminescence of Pr, Nd, Ho, Er, Tm, and Yb in CdS, and Ho, Er, Tm, and Yb in ZnSe has been observed from crystals Prepared by diffusion using rare earth metals and an excess chalcogen pressure. For a given temperature, time, and chalcogen pressure the spectral characteristics were very reproducible from run to run, and the emission intensity for Nd, Er, and Yb in CdS was as high or higher than the best vapor phase doped crystals we have grown. For a few rare earths it was found that certain conditions of diffusion tend to yield optimum rare earth emission intensity with respect to the background lattice emission. Photoluminescence measwements of Yb in CdS as a function of depth gave a profile which was neither a Gaussian nor complementary error function. Part of the profile appears to arise from a fast component of the diffusion and the other part from a slow diffusing component. At 960°C and 33 atm S pressure, a com -plimentary error function approximation of the slow diffusing component gave a diffusion coefficient of D = 1.3 x 10-9 sq cm per sec. MOST of the studies of emission from rare earth ions in II-VI compounds have been reported on crystals doped during growth,1,2 although Kingsley and Aven prepared ZnSe:Er by diffusion for paramagnetic resonance and fluorescence studies. Pappalardo and Dietz prepared CdS:Yb by diffusion, but they made optical absorption measurements., We know of no study on the properties of rare earth diffusion in the II-VI compounds. To date we have diffused Pr, Nd, Ho, Er, Tm, and Yb into CdS, and Ho, Er, Tm, and Yb into ZnSe and observed the rare earth emission spectra. For a given temperature and chalcogen pressure, the emission characteristics are very reproducible from run to run and for Yb, Nd, and Er in CdS, as good as the best crystals we had prepared by doping during vapor phase growth.2 The emission of Pr, Ho, and Tm has been observed in CdS prepared by diffusion for the first time. Previous attempts2 to prepare these later three materials by vapor phase growth were unsuccessful. The problem of obtaining reproducible characteristics in II-VI semiconductor compound work is well known.5 Not only is it difficult to reproduce results from one laboratory to another but it is sometimes difficult to reproduce results from one growth run to another under ostensibly identical conditions within one laboratory. This situation has been particularly bothersome in research on the luminescence of rare earth activated ZnS1 and Cds2. Crystals from one vapor phase growth run would show very strong rare earth line emission while crystals from a nearly identical run would show no rare earth emission. It was also observed on occasion that the intensity of the rare earth emission was not constant over the entire volume of a single crystal. MATERIAL PREPARATION AND INSTRUMENTATION Vapor phase grown boules of CdS were supplied by Dow Corning. This material was characterized by a free electron concentration of n - 3.5 x 1015 cm-3 and Hall mobility of 350 sq cm per v sec at room temperature. There were microscopic voids and decorated precipitates in some samples. The precipitates annealed out at diffusion temperatures but the voids remained. Single crystal rectangular samples of mm dimensions were sawed from the boules. The ZnSe was polycrystalline, UHP grade from Eagle-Picher. Poly-crystalline samples were sawed from the ingots. The samples were lapped, polished on one side, etched in a solution of 0.5 M K2Cr2O7 in 16 N H2SO4, and thoroughly washed in distilled water. A sample, excess sulfur (or selenium), and 5 mg of rare earth metal (turnings) were sealed in a 3.6 cm3 quartz ampoule at about 2 X 10-5 torr. The high chalcogen pressure used (1 to 30 atm) prevented thermal etching of the crystals and affected the diffusivity and solubility of the rare earth ions in the crystal lattice. For meaningful or reproducible results, it is thus necessary to specify the vapor pressure at which the diffusion was carried out. It is assumed that a negligible amount of the chalcogen was used in the formation of rare earth sulfides or selenides Our sulfur vapor pressure calculations are based on data assuming S2, S6, and S, molecules only in which case the equilibrium constants are given by6 where the pressures are expressed in torr. Selenium vapor consists of a mixture of Se2, Se4, Se6, and Se6 molecules. The selenium vapor pressure was calculated using equilibrium constants given by The status of the rare earth source during diffusion is unknown, i.e., the partial pressures of the rare earth metal and of the rare earth chalcogenides has not been determined. All emission spectra were recorded at 77°K on a Perkin-Elmer model 98-G spectrometer using a 640 line per mm grating. No correction was made for the spectrometer and detector spectral sensitivity. Excitation was by means of an XBO 1600 w xenon arc

Jan 1, 1970

By Shawn T. Sorrell, Carl Hrovatic

Original by Carl Hrovatic and Shawn T. Sorrell Revised by Carl Hrovatic Land is a precious resource and should be treated as such by all members of our society. The soil covering this earth is only a very thin outer layer, varying in thickness from a few inches to a few feet and covering the rocks and minerals lying beneath the surface. The wise use of this valuable commodity is the responsibility of everyone. Many everyday activities disturb the earth's surface. Examples are highway construction, housing and commercial developments, agriculture, and various types of mining. This chapter discusses the relationships of the environment to land as it applies to surface operations in the coal industry. Mining by surface methods disturbs, for a brief period of time, thousands of acres of land annually. In addition, refuse piles, slurry ponds, abandoned mine structures, unprotected mine openings, and unsightly cleaning plants can also adversely affect land unless properly handled. ACTIVE SURFACE MINING OPERATIONS Mining by surface methods includes rock quarries; sand and gravel pits; huge open pits to extract iron, copper, phosphate, and other ores; and coal mining. Production of coal by surface methods is now approaching 408.2 Mt/a (450 million stpy), amounting to almost 60% of the total coal output. Surface coal mining can be classified into the following five broad categories : Open-pit mining is practiced where coalbeds are extremely thick, as in some western states, or where coalbeds are sharply pitching, as in the anthracite region of the eastern United States. A typical open-pit mine, with coalbeds of 3.05 to 30.5 m (10 to 100 ft) or more thickness and a

Jan 1, 1981

By Walter Craft, John L. Lamont

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test' and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann's principle2 for calculating hardenability from chemical composition; and Field's conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By John L. Lamont, Walter Craft

Adequate hardenability has long been recognized as one of the first requirements for producing desired mechanical properties in a heat-treated steel. Since the introduction of the Jominy end-quench test' and the development of correlative information to expand its use, industry has had an effective measure of hardenability. Prediction and control of the hardenability have been made possible by Grossmann's principle2 for calculating hardenability from chemical composition; and Field's conversiona from depth of half-martensite hardening to Rockwell C hardness has made the relation more quantitative. These developments have facilitated the design of new steels and the control of standard grades to the extent that it has been possible to establish tentative hardenability bands for some of the more commonly used alloy steels.4 As the depth of hardening of the Jominy test specimen is usually measured by Rockwell C hardness, it was considered that it should be possible to predict the hardness by a more direct calculation. It has been found that this can be accomplished by the addition of Rockwell C units proportional to the carbon and alloy content, grain size, and position in the Jominy test specimen. The calculation has been found to be fairly accurate, and because of its additive character is relatively simple to use. In principle the method of calculation is somewhat similar to the expressions developed by Herty, McBride, and Hollen-back,5 Burns, Moore, and Archer,= and Burns and Riege1.l The calculation is started from a base that includes the effects of carbon content and position in the Jominy test speimen. Rockwell C units are added to the base in proportion to the alloy content and grain size. This sum represents the Rockwell C hardness up to the level at which a disproportionate increase of hardness is caused by the formation of martensite, and above this level an increment for martensite hardening is added. The effects of alloys are directly proportional to the amounts present and are independent of each other, the carbon content, and the position in the specimen. Furthermore, the factors for determining the martensite increment are dependcnt only on carbon content and are independent of cooling rate and alloy content. It is this absence of interrelation between the different factors that makes it possible to calculate the hardness and makes the method of calculation consistent with the principle that the character of the hardening reaction is governed primarily by carbon and that alloys exert their effect chiefly through control of the critical cooling rate. The principle of the calculation, and the effects of alloys on the critical cooling rate,

Jan 1, 1947

By J. J. Beeson

Page I. PrimaRy MineRalization............................................ 356 1. Introduction..................................................... 356 a. Scope of Work............................................... 356 6. Acknowledgments............................................ 357 c. The Bingham Mining District.................................. 357 d. General Geology.............................................. 357 e. The Utah Copper Mine....................................... 376 f. Field and Laboratory work.................................... 376 2. The Quartz-Monzonite.............................................. 377 3. The Pegmatite Veins.....:.•..............................:........ 378 4. The High-Temperiture Veins.........................-.............:379 5. The Early Hydrotherma! Period.:......................'............ 380 6. The Late Hydrothermal Period................................:.... 385 II. Seconuabx EnricuMENT............................................. 386 . 1. Author's Note;..... ;............................................ 386 2. Factors Governing Enrichment.....................................: 387 3. The Enrichment.................................................... 387 4. The Covellite Enrichment.; .:; ; : .:. :..:.............:................ 388 a. The Capping above the Covellite Ores:....:....................... 388 b. Conclusions Drawn. from a Study of the Capping and the Covellite ; Ores....,.............................................:.....,.' 392 c. Covellite Enrichment at Depth......:......................... : : 392 5. The Chalcocite Enrichment...................................... ; 394 a. The Carbonates in the Capping above .the Chalcocite Ores...:..: .. 394 ' b. The Formation of Chalcocite..:.:. :......:..'...........,......' 394 . 6. Secondary Chalcopyrite and Bornite.............................i ..., . 395 111.- Conclusions as to the Formation.oF the ImpoRtant Sulphides in the Disseminated ORes........................................,.......... 400 I. Primary MiNeRalization 1. Intrdtiction a. Scop. e .of Work.. first part bf, this paper deals with the country rock, its pegihatitic, pneumatolytic', and hydrothermal altektions; also, the effect of magnetite on the deposition of the primary chalcopyrite and pyrite.

Jan 1, 1916

By Yingchang Tsenshan Wang

UUIN L&SS 1» Paqb I. Introduction........................................................658 1. Subject and Scope...............................................658 2. Acknowledgments...............................................659 3. Review of Previous Work........................................659 Field Data...................................................659 Experiment.a1 Data............................................662 4. Plan of Present Investigation.....................................662 Method of General Procedure...................................663 I1. Experimental Work..................................................663 A. The Solution of Sphalerite..............................:........663 1. The Solvent Effect of Iron Sulphates upon Sphalerite...........663 2. The Solubility of Sphalerite in Salt Solutions of Silver, Copper and Lead...............................................668 B. Formation of Zinc Carbonates....................................674 3. The Reactions of Carbonates and Bicarbonates With Solutions of Zinc Salts............................................674 4. The Reaction of Zinc.Sulphate Solution With Limestones.......684 C. Peculiar Conditions Affectitig the Formation of Zinc Silicate (calamine) and Zinc Carbonate (smithsonite)..........................686 5a. The Effect of Carbon Dioxide Upon the Basic Silicate and the Carbonates of Zinc in Water, and Its Bearing Upon the Conditions of Theii Precipitation..............................686 5b. The Reactions of Solutions of Soluble Silicate With calamine and Smithsonite in Solution in Presence of Carbon Dioxide..689 6. The Reactions of a Mixture of Hydroxide and Silicate of Sodium with a Dilute Solution of Zinc Sulphate...................691 D. High-Temperature Methods.....................................692 7a. The Influence of Temperature on the Formation of Calamine..692 7b. Possible Effect of Heat on Calamine and Srnithsonite.........697 E. Summary of the Experimental Work..............................698 III. Petrographic Work....................................................700 1. The Occurrence of Sphalerite in Limestones or in Cherts............701 Summary of the Blende in Limestones and in Cherts.............7432 2. The Partially Altered Sphalerite and the Oxidation Products........702 a. Smithsonite with Blende....................................702 b. Calamine with Blende......................................703 c. Smithsonite and Calamine..................................703 d. Summary on the Partially Altered Sphalerite and Its Oxidation Products..............................................704 IV. Concl~~siom ........................................................-705 V. Microphotographs and Photographs with Their Explanations.............705

Jan 1, 1916

By P. Payson

INTERGRANULAR corrosion in corrosion-resistant chromium-nickel steels has been widely discussed in the last few years. So far as the author knows, nothing has been published which definitely shows that this tendency can be eliminated, although suggestions have been made that a remedy is possible if certain specifications are satisfied. Strauss, Schottky and Hinueber1 suggested an increase in chromium content to an extent that would prevent the impoverishment of chromium on carbide precipitation sufficient to cause impaired corrosion resistance in the matrix. Pilling2 suggested an increase in nickel, so that the stability of the austenite matrix would be increased. Aborn and Bain,3 say that "intergranular attack-may be eliminated by preventing carbide precipitation (e. g., by lowering the carbon content or somehow raising its solubility) or by precipitating it permanently under conditions which will not remove chromium from solid solution so drastically at any points." In a later paper Aborn and Bain4 state that many different metallic elements, tungsten, vanadium, copper, aluminum, molybdenum, titanium and zirconium, have been added in small per-centages to increase the stability of these alloys, but that it has been reported that according to the copper sulfate test these added elements act only to retard the intergranular corrosion, and that increased nickel and chromium contents have similar effects. Newell5 showed that the lower the quenching temperature before reheating, the less severe was the intergranular attack.

Jan 1, 1932

By H. D. Kynor

By the term mechanical mining is meant that operation, or series of operations, that replace the hand methods of mining. The first undercutting machine to operate in anthracite was placed in the Butler mine of the Hillside Coal and Iron Co., Dec. 23, 1910, by the Sullivan Machinery Co. The first Jackhamer used in the anthracite field was installed at the Wadesville colliery of the Philadelphia & Reading Coal and Iron Co. in Oct., 1912, by the Ingersoll-Rand Co. The first longwall conveyor was installed at the Dodge mines of the Delaware, Lackawanna, & Western Coal Co. in March, 1912. The first mechanical scraper equipment was installed in the Seneca mines of the Lehigh Valley Coal Co. in January, 1914. The amount of anthracite mechanically mined since the first mining machine was installed in 1910" is as follows: Penna. Coal Co. D. L. & W.. ScRanton Temple Hudson YeaR and Hill- Tons Coal Co., Coal Co., Coal Co., Total, side Coal Tons Tons Tons Tons and Iron. Tons 1920................ 372,737b 367,000d 322,892 74,127 371,878 1,508,634 1919................ 950,786 no record 306,616 81,575 319,356 1,658,333 1918................ 917,778 744,966 24,880 44,756 288,781 2,021,161 1917................ 757,940 838,800 5,050 57,279 164,180 1,823,249 1916................ 286,780 860,663 13,960 114,173 101,475 1,377,051 1915................ 428,819 592,169 8,253 1,029,241 1914................ 219,188 153,896 373,084 1913................ 171,505 1912................ 124,267 124,267 1911................ 40,319 40,319 1910................ 1,184 1,184 a A slightly greater production was obtained than here indicated, as the tonnage from individual operations is not shown. b Decrease due to strike conditions in 1920. c Does not include tonnage of D., L., & W. d D., L., & W. decrease in 1920 due to having fewer mining machines in operation. There are about 150 undercutters in use in the anthracite region, 80 mechanical loaders, and 10 longwall conveyors.

Jan 1, 1922

By J. B. Mudd

Introduction It is difficult to think of any activity on which mankind has been more dependent than mining, and certainly there is much evidence in almost every part of the world of old workings that clearly demonstrate that man from earliest times has dug and toiled to take from the earth precious stones, metals and materials that from time to time have been essential or of value to him. In step with social development and industrial and technological advances the tempo of mining activity, regulated only by the laws of supply and demand, has quickened and in this century has accelerated rapidly in keeping with its dramatic development. Indeed, the rate of change of events has been such that if it were to continue to accelerate as fast as it has over the past decade there is reason to wonder how the insatiable demands for metals and minerals are to be met in the years that lie ahead. Shallow mines containing high-grade ore deposits either have been or are being rapidly mined out and their place can only be taken in general by ore lying at greater depth, or by ore of low grade, situated for the most part in remote and in underdeveloped areas. The cost of exploration and development is rising at an alarming rate, with the result that the expenditure now required to bring a mine to production far exceeds anything previously contemplated. It is estimated that the total capital required to maintain existing operations and develop new ones during the next 5 years will be of the order of $50,000 million and of this, new capital to bring new mines to production will be of the order of $3,000 million. Today no single mining finance company can, from its own resources, find all the money for a major mining development, and as a consequence there has been a strong trend toward joint ventures and to the formation of multinational consortiums. International lending institutions already play an important part in financing many new mining projects and their participation provides the financial umbrella under which other lenders can invest with greater security. There is little doubt that to finance the costly ventures in the future, governments and international lending agencies, banks and finance

Jan 1, 1971

By R. F. Mehl, G. V. Smith

THE decomposition of austenite in steels, because of its immense practical importance, has been subjected to extensive study in recent years from the point of view of the mechanism of the process.1-3 Although much information has been acquired, a number of questions, principally of theoretical interest, remain. One is that of the atomic-crystallographic mechanism by which each of the various reaction products forms. The isothermal reaction products of the eutectoid decomposition in plain carbon steels (to which this study is restricted) have conveniently been classified in three general groupings-pearlite, bainite, and martensite. Of these several products, pearlite and martensite have been studied extensively, but bainite has received only scant attention. As a result, the mechanism of the formation of pearlite and that of martensite are now fairly well understood while a great deal of uncertainty exists regarding bainite. PEARLITE Pearlite forms from austenite by the precipitation of alternate platelets of cementite and ferrite, which grow into the austenite matrix .2-5 The rate of reaction may be described in terms of a rate of nucleation and a rate of growth.2.3 Mehl and Smith6 have attempted to determine the lattice relationships existing between the ferrite in pearlite and the parent austenite. Using a pole-figure method of analysis, it was found that a limited number of ferrite orientations resulted from the decomposition of a single grain of austenite; it was not possible, however, to decide between two assumed ideal relationships, both of which appeared to account for the experimentally determined pole figure. It was definitely shown, however, that the relationship obtaining was quite different from that determined for the proeutectoid separation of ferrite.7 No attempt was made to determine the habit plane (matrix plane to which the precipitate lies parallel) of the pearlite lamellae. Belaiew8 earlier had stated that the number of directions assumed by the pearlite lamellae in a single grain of austenite was 12 (no details were given) and concluded wrongly, as Mehl and Smiths have pointed out, that the lamellae delineate the [210] planes of ferrite.* MARTENSITE It is known that martensite is a transitional constituent of body-centered tetrag-

Jan 1, 1942

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP' have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

By O. P. Arora, M. Metzger, G. R. Ramagopal

Single-phase aluminum containing 0.0001 to 0.06 pct Cu was studied in strong acid, mainly through observations of hydrogen evolution. The strong influence of copper was exerted almost entirely through the imposition after a certain delay time of an auto-catalytic localized-corrosiott reaction. Additions of cupric ion to the acid produced lower accelerations. The significance of the quantity and distribution of copper was discussed, and the implications for intergranular corrosion and neutral chloride pitting were indicated. AN investigation of intergranular corrosion in single-phase high purity aluminum exposed to hydrochloric acid indicated the copper content of the metal to have an influence on corrosion at lower levels than previously suspected.&apos; The work reported here was a closer examination of the action of copper but dealt with general corrosion to gain the advantage of having a continuous measure of corrosion through the volume of hydrogen evolved, the reduction of hydrogen ion to hydrogen gas being the principal or only cathode reaction in strong hydrochloric acid. Previous work on the hydrochloric acid corrosion of aluminum was sometimes insufficiently structure-conscious and the need for care in evaluating it arises from the low solubility of the iron impurity,&apos; and of some alloying elements, and the known or possible presence in many of the compositions studied of second phases leading to greatly increased corrosion rates.3 These increases are attributed to the presence of low hydrogen-overvoltage cathodes provided by the second phase.3&apos;4 For the present single-phase work, a few studies which used high-purity base material and small copper additions5-&apos; provide the essential information most unambiguously. The corrosion rate was shown to be increased markedly by the introduction into the acid of small quantities of the ions of copper (and of certain other metals) which cement on the aluminum and provide cathodes of low overvoltage.5 When there was sufficient copper in the aluminum, the same result was produced during the course of corrosion leading to a rate which increased with time as the reaction was stimulated by one of its products (autocatalytic reaction). In 2N (7pct) HC1, an accelerating rate was observed at 0.1 pct Cu but not at 0.01 pct.5,7 The present work dealt with corrosion rate and morphology and their correlation with the quantity and distribution of copper catalyst for copper contents from 0.0001 to 0.06 pct. PROCEDURE A lot of high-purity aluminum containing 0.0021 pct Cu, 0.001 pct Fe and 0.003 pct Si (Alloy A) was alloyed with copper to yield aluminum containing 0.014 pct Cu (B) and 0.06 pct Cu (C). Later it was found necessary to include the lower copper Alloy K which contained 0.0001 pct Cu, 0.0004 pct Fe and 0.0004 pct Si. The upper limit for any other element can be confidently estimated as 0.0005 pct. No element other than copper appears to be present in quantities sufficient to have an effect on general corrosion as great as the observed effect of the copper in A, B, and C. The only other heavy metal detected by spectrographic examination was silver (< 0.0001 pct). The acid was made up from a selected lot of 37 1/2 pct CP hydrochloric acid containing 0.1 ppm heavy metals (mainly Pb), 0.05 ppm Fe, and < 0.008 ppm As and from water distilled from 1 megohm-cm demineralized water and believed to have contained negligible quantities of heavy metals influencing corrosion. Acid strength was adjusted to within 0.05 pct HCl of the stated value by using precision specific gravity measurements. Test blanks 10 by 41 mm were sheared from 1.65-mm cold-rolled sheet. Edges were finished by filing. The blanks were annealed in air at 645°C for 24 hr in alundum boats and rapidly water quenched. The anneal is thought to have produced a substantially homogeneous solid solution—for iron, copper, or silicon, for example, the annealing temperature was 200°C or more above the solvus-and the quench is considered to have preserved the high-temperature structure except for the condensation of lattice vacancies into dislocation loops.&apos; The 0.06 pct Cu alloy did not appear unstable in respect to slow precipitation reactions at room temperature since two pairs of tests failed to show significant differences between specimens heat treated 3 1/2 years earlier and specimens heat treated 1 or 2 days before.

Jan 1, 1962

By R. R. Boucher, O. J. C. Runnalls

A pronounced thermal effect has been observed on heating or cooling a1wninum-rich Al-U and Al-Pu alloys. From microscopic and X-ray diffractionstudies, the effectl has been attributed to trnsfor)nations in the inlemetallic phases UAl, and PuAl , involuing rearrangement or cluslering of vacancies The transformation obsrved in Al-20 wi oct U alloys occurred near the a Al-UAl4 eutectic tem-perature of 646°C making it difjicult to detect from heating curves. When cooling, howeoer, thermal mad X-ray analyses indicnted that the high-temperati~re phase labeled p UAL, precipitated initially during euitectic solidification. As solidification continued and after an induction period o-f 5 lo 20 tnin the nu-cleatiorz and growth of the low- twmperature phase, a UAl4 produced an euolution of energy which raised the observed alloy temperature by 1° to 2°C. in Al-Pu alloys the transformation occurred at 645°C, 5 deg below the eutectic solidification temperccture. The eslimated latent heat of transformation was 25 +5 cnl per g PuAl,. The high-tetnpevcl-ture forms of UAl, and PuAl, were easily 9-etccined by chill casting Al-U and Al-Pu alloys and on reheating the alloys the trcltzsforrnation to the a phase was sluggish even above 600°C. Separated single cryslals o-f UAl4, joy example, showed no evidence Of transformalion after heating for 16 hr at 620°C. The transformation rates increased yapidly enough with increasing temperature, however, that a a spontaneous liberation of energy lens observed on occasion when bealing cast Al-20 wt pet U to neal- the RECENT phase studies on A1-Pu alloys have indicated that earlier reported equilibrium diagrams should be modified to take account of several poly- morphic transformations in the intermetallic compound PuAl,.&apos; During the course of the latter work an unexpected heat evolution was observed while cooling a solid alloy consisting of a mixture of a aluminum and PuA1,. The evolution occurred at 645°C, y below the a A1-Pu A1, eutectic solidification temperature. Subsequent thermal-analysis experiments with A1-U alloys showed that heat was evolved there also at a temperature nearly coincident with the a A1-UA1, eutectic solidification temperature of 646°. A search of the literature revealed that similar thermal effects had been observed before for both A1-U and A1-Pu but had never been fully explained.2,3 The purpose of the present paper is to describe thermal-analysis and X-ray diffraction experiments which have led to the conclusion that the thermal effects are due to transformations which involve the rearrangement of vacancies in the intermetallic compounds UA1, and PuA1,. EXPERIMENTAL PROCEDURE The A1-U alloys were prepared by heating super-pure aluminum (99.99 pct +) obtained from the Aluminum Co. of Canada in a graphite crucible surrounded by an induction coil. At 1000°C high-purity uranium metal produced by the Eldorado Mining and Refining Co., Ltd. was dropped into the liquid aluminum and was dissolved completely within 15 min. The impurities in the uranium were A1—4 ppm, Ca-4, C-70, Cr-3, Cu-6, Fe-30, Mg-2, Mn-10, Ni-25, Si-25, and Zn-2. The A1-Pu alloys were prepared by reacting plutonium dioxide with liquid aluminum under cryolite (3 NaF . AlF,) for 10 min at 1100°C in graphite crucibles exposed to the air. The plutonium was 99.8 pct pure, containing trace impurities of Ca, Cu, Fe, Pb, Si, and Zn. The liquid alloys were usually poured into water-cooled molds to provide castings of uniform composition from which samples could be cut for heat treatment and thermal-analysis experiments.

Jan 1, 1965

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Cyril Wells, Robert F. Mehl

The practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out.l,13 This importance lies chiefly, though by no means only, in the study of carbufizing and in the study of reactions involved in the eutectoid inversion in steel. The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in ?-Fe and their mutual effects are measured with precision. The present paper reports the results of measurements of diffusion coefficients D of manganese in ?-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients.‡ Data on the rate of diffusion of manganese in ?-Fe have been reported by Fry2 and by Paschke and Hauttmann.3 Claussen4 calculated the diffusion coefficient D from Fry&apos;s data as 3 X 10-10 sq, cm. per set. at 960º, which will be shown to be incorrect by many orders of magnitude. Paschke and Hauttmann gave a rough value of 9.6 x 10-8 Sq. cm. per set. at 14000. Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon. Method and Materials Method.—The method employed is identical with that used earlier.5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded. The diffusion anneals were performed in argon, except One (test 18) in which hydrogen was employed for purposes noted below. The temperatures reported are accurate to about 3" and constant within 1°C; the diffusion times are reported to the nearest half hour. The specimens were furnace-coo1ed after the diffusion ation, at about 2° per min. Layers, usually 0.004 in. thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0.I Per cent Mn; the distances of these layers from the interface was measured to ±0.0002 in. The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions.8 The D values calculated by these two methods do not differ appreci000. The Grube solution was used except in tests in which the effect of concentration upon D was greater than so per cent; in such cases the Matano method, which explicitly provides for the variation of D with concentration,&apos; is the more reliable. In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer. In 3 of the 3&apos; tests, however, this is not justified, and the D values

Jan 1, 1941

By Perry G. Harrison

The first autlientic description of an iron bath for the deposition of iron is probably that of Bottger in 1846, who used a bath containing ferrous sulfate and ammonium chloride. In 1861, Kramer deposited iron from ferrous chloride solution. Electrolytic iron was produced in 1869 by Bietz, who used it for making some magnetic tests. In the same year, Klein is. said to have worked out his process. Jacobil in 1869 described the results obtained in electroplating with iron on copper for making dies and plates for bank notes, by Klein&apos;s process. A letter from Klein to Jacobi describes the bath more fully. It consisted of FeS04 + (NH4)2SO4. Lenz2 described some properties of electrolytically precipitated iron. He used Klein&apos;s bath, FeS0, + MgSO4 + MgCO3, to neutralize and obtained fine-grained and hard iron. His conclusions were as follows: 1. Electrolytic iron and copper contain gases, notably hydrogen. 2. The volume of gas absorbed by iron varies within wide limits, but it is easy for iron to take up very considerable quantities of gas. 3. The absorption of gas is principally in the first formed layers of iron. 4. When iron is heated, gas begins to come off below 100°, principally hydrogen. 5. Heated to redness, reduced iron oxidizes in water, in part at least at the expense of the oxygen of the water, decomposing it and setting free hydrogen, which is partly or wholly absorbed. Siemens,3 in 1889, was the first to propose a general process embodying a step for leaching a sulfide mineral with ferric chloride or sulfate and a step for regenerating the leach and depositing iron on a cathode in a diaphragm cell. So far as is known, Siemens did not carry out his patent

Jan 1, 1930

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.&apos;-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc&apos;s were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By Norman B. Pilling

The technical difficulties hampering the metallographic analysis of silicon steels are chiefly the result of the extreme corrodibility of these alloys. The addition of silicon to iron in increasing quantities, up to about 6 per cent., rapidly increases the susceptibility of the alloy to chemical attack, not only in acid solution, but in water. This renders the preparation of metallographic sections very difficult, because of a non-selective attack upon the finely polished surface by the water used as a lubricant in polishing. This water attack masks the true structural details revealed by suitable etching reagents. It is thus necessary to use alcohol as a polishing lubricant in the last stages of preparation and to avoid all etching reagents having an aqueous base. A specific reagent for the identification of iron carbide in ferrous alloys, and the one hitherto used almost&apos; exclusively by metallurgists, is an alkaline aqueous solution of sodium picrate, which stains this constituent selectively. Its application to silicon steels has not proved successful, as its distinctive selective action is more or less completely hidden by the general attack of the aqueous solvent on the silico-ferrite, greatly accentuated by the fact that this reagent must be used at its boiling temperature (105&apos; C.). Thus, a powerful metallographic aid to the study of the higher silicon alloys, such as transformer steels, is lost. A new reagent has been developed for the purpose of overcoming this difficulty. It is with some hesitation that the list of etching reagents, already overburdened, is increased, but the properties of this new reagent are advantageous in several ways and a definite field for it may be found in the metallography of ferrous alloys. The reagent consists of a dilute solution of nitric acid and methyl alcohol in nitrobenzol. It is a great advantage to secure an anhydrous solution, as a tendency toward acidic etching has been traced to small amounts of water. A convenient method of preparation is to make an anhydrous stock solution of nitric acid in methyl alcohol in the proportion 20 per cent. acid by weight (12.5 per cent. by volume). The alcohol can

Jan 1, 1924