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By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3'4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By J. M. Roberts, D. M. Barnett

The activation energy required to break a pinned dislocation line away from its condensed atmosphere of impurity atoms is calculated as a .function of applied stress, without neglecting line tension. Reasows are presented for not assuming the effect of line tension to be negligible when considering the problem of freeing a small segment of dislocation from an impurity atmosphere. The dislocation is considered to he pinned at each atomic size along its length and the pinning points are assumzed immobile. The development is a refinement of the origznal cottrell-bilby1 theory. The solution is compared to recent approximations developed by cottrell3 and Haasen5 in which line tension con- IN 1949 Cottrell and bilby1 considered the problem of determining the force required to pull a dislocation away from its condensed atmosphere of impurity atoms. They also examined the effect of thermal fluctuations on this force. The dislocation line was pictured as bowing out in a triangular loop under the action of an applied stress, and the activation energy necessary to free the dislocation from its atmosphere was calculated as a function of stress, line energy, and dislocation-solute atom interaction. siderations were neglected. A qualitative explanation of the yielding process in terms of the activation of Frank-Read sources is presented, but the lack of a realistic solution to the dynamic dislocation problem involved prevents an extension of the model at present. A self-consistent correlation between the present calculations and experimental data for delay time associated with yielding and the temperature dependence of the upper yield stress was made. Favorable agreement was noted. It is concluded that extension of the original Cottrell-~ilby' theory which includes line tension effects can just as well describe the yielding process as other approximations3,5 which neglect line tension. Cottrell and Bilby found the form of the activation energy vs stress curves to be almost independent of the line energy and the interaction energy (i.e., these parameters only affected the activation energy U by a scale factor). A check of the theory was accomplished by comparison with the experimental data of McAdam and Mebs2 for the lower yield stress as a function of temperature. cottrell,3 in 1957, attempted to obtain a simple closed-form solution for the activation energy as a function of stress by linearizing the quartic equation relating displacement of the dislocation line and applied stress. It was argued that since the contribution to the line energy/atomic plane of a dislocation is made by the long-range stress field of the dislocation through a term of the type (Gb3/2p)ln A/ro, where

Jan 1, 1963

By M. T. Simnad, C. E. Birchenall, M. H. Davis

The transport mechanisms previously proposed in wustite and hematite have been confirmed by movement of inert markers during the growth of these phases. By similar measurements the mechanism for magnetite has been determined. The rates of growth of multilayer scales on iron, magnetite and hematite on wustite, and hematite on magnetite have been measured. All rates are found to be diffusion controlled under the conditions of the experiments. MANY studies have been made of the rate of oxidation of iron in both the low temperature, film-forming region and the high temperature scaling range. The interpretation of the results has been greatly complicated by the formation of multi-layered scales containing the various phases of iron oxides. In most cases no attempt has been made to determine the composition of the scale and its dependence on time of oxidation in a quantitative manner. However, several recent studies'" have taken this variable into account. It is generally agreed that the growth of thick scales on iron follows a parabolic rate law for the increase of total thickness. In the thin film region agreement has been claimed with parabolic equations of various forms and with logarithmic equations. The discussion here will be concerned only with the formation of scales of considerable thickness, greater than several microns, although some of the conclusions may be applicable to thin films. A brief survey will be given of the solid phases of the iron-oxygen system, the stability of wiistite in bulk and in thin films, the relative densities of iron in the metal and oxides, and the kinetics of forma- tion of oxide scales on iron. New experimental results will be introduced at several points during the discussion, and an attempt will be made to formulate a mechanistic picture consistent with these observations. The experimental techniques are described in an appendix. Iron-Oxygen System Fig. la shows the iron-oxygen phase diagram. Wüstite ("FeO"): The lowest of the oxides has a NaCl type cubic lattice formed by close-packing of the relatively large oxide ions with the smaller iron ions arranged in the interstices. The ionic radius for 0' is about 1.3 A, while Fe++ has a radius of about 0.8A and Fe"' about 0.7A. Its range of existence on the phase diagram is very wide for an ionic material of this type and does not seem to include the stoi-chiometric composition FeO. These deviations appear to be well established as vacancies on iron lattice sites by the comparison of lattice parameters and densities for a series of compositions by Jette and Foote.4 The limits of the field are disputed, but the work which seems most reliable" indicates vacancies in from 5 pct to more than 12 pct of the iron sites. In order for the crystal to be electrically neutral, there must be electron holes which correspond to the formation of trivalent iron ions equal to twice the number of vacancies. Magnetite ("Fe³O4"): Considerable disagreement also exists in the literature about the stable range of the Fe³O4 field. Some diagrams show the Fe³O4 composition to be lower in oxygen than the formula indicates, but Schenck6 gives a diagram from the

Jan 1, 1952

By P. M. Robinson, M. B. Beaer

The heat of formation at 0°C of the intermetallic compound AgMg as a function of composition has been determined by tin-solution calorimetry. In this technique, the heat of formation is determined as the difference in the heat effects, at infinite dilution, on dissolution of the compound and a mixture of its components added alternately to liquid tin from a reference temperature, such as 0°C. The experimental technique and method of calculation have been described elsewhere.' The compound AgMg is a 0 electron compound with a CsCl structure.2 In nonstoichiometric compositions of the compound, atoms of the excess component are substituted on the AgMg lattice.3,4 The homogeneity range is approximately 43 to 52 at. pct Mg at room temperature and 38 to 65 at. pct Mg at 500Oc.2 Single-phase alloys outside the homogeneity range at room temperature can be prepared by quenching. The specimens used in this investigation contained from 39.0 to 54.8 at. pct Mg. They were made available, together with analyses, by the Research Laboratory of the General Electric Co. Metallographic examination of the quenched specimens containing 39.0 and 54.8 at. pct Mg gave no indication of the presence of a precipitated phase. The measured heats of formation are listed in Table I. In a calorimetric run, four to six additions each of a specimen and the corresponding mixture of the components were made. One or two calorimetric runs were carried out with each composition depending on the amount of samples available. The limits stated in the table represent the experimental precision and not the absolute accuracy of the measurements. Thermodynamic investigations of the compound AgMg have been made by Trzebiatowski and Terpilowski 5 and Kachi.6,7 The heats of formation at 500°C derived from the combined electromotive-force values of these investigators8 are more exothermic than the heats of formation at 0°C reported here, Fig. 1. The differences cannot be explained by the difference in temperature. This is shown by the published heat capacity of the stoichiometric compound, which obeys the Kopp-Neumann rule from 0" to 500oC.9 The heats of formation derived from equilibrium data are generally considered to be less accurate than those determined by calorimetric methods because small errors in the change of the equilibrium values with temperature have a large effect on the calculated value of the heat of formation. The heats of formation derived from the combined published electromotive-force values reach a maximum at 56.0 at. pct Mg.8 Kachi reports a maximum of -4.7 kcal per g-atom at the stoichiometric composition.7 The present results also indicate a maximum at or near the stoichio metric composition, Fig. 1.

Jan 1, 1964

By Robert I. Jaffee, Bruce W. Gonser, Eugene M. Smith

THERE has been little investigation of the gold-germanium binary alloys. Haughton1 does not mention any work on the system. In a review article commemorating the fiftieth anniversary of the discovery of germanium, E. Einecke2 mentioned a gold germanium eutectic at 24 atomic per cent Ge (10.4 weight per cent) melting at 359°C., but did not give the source of his information. From measurements of electrical conductivity, J. 0. Linde3 estimated that at least o.6 weight per cent germanium is soluble in gold. The recent availability of germanium in this country in commercial quantities has led to interest in its properties and its alloys. This study is part of a program of investigation on germanium alloys; work on ternary alloys involving germanium and gold will be reported later. In this investigation, the composition and melting point of the Au-Ge eutectic reported by Einecke has been found to be substantially correct. Eutectic composition has been placed at 12,0 per cent germanium, however. An alloy of 10.4 per cent Ge, Einecke's value, was found to have a few gold dendrites in it. The eutectic temperature has been determined as 356.0 ± 0.5°C., slightly less than the temperature of 359°C reported by Einecke. The liquidus curves and the solid solubility of germanium in gold have been determined, and are shown in Fig. I. MATERIALS AND ALLOYING The germanium used in this investigation was prepared by the Eagle-Picher Lead Co. from pure germanium oxide, by reduction in clay crucibles with sodium cyanide. The regulus is quite pure, assaying over 99.9 per cent Ge. High-purity gold obtained from Handy and Harmon was used. Alloying was carried out in graphite crucibles in an atmosphere of purified hydrogen. The temperature was brought up to 1050° to 1100°C., and the metal was allowed to freeze in the crucible. Prepared in this way, the gold dendrites in hypoeutectic alloys were somewhat segregated at the bottom and sides of the ingot, and on the hypereutectic side the lighter primary germanium tended to gather at the top. Most of the alloys were made from virgin metal. Low-germanium heats were made by alloying pure gold with the eutectic. Melting losses were consistently a few milligrams or less, and the composition could safely be taken from the intended analysis. The 30 per cent and 50 per cent germanium heats for thermal analysis were made in part from remelted higher germanium heats, and they may be off composition as much as one per cent. Because of the high cost of materials, the weight of heats for thermal analysis were 15 to 20 grams and heats for metallographic, X-ray, and hardness specimens were 2 to 4 grams.

Jan 1, 1945

By D. M. Davidson

The drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company's standard core-drill outfits to complete 44 holes to an average depth of IIO ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered and is drained by the Piney and Tye Rivers, which are tributary to the James. Geology The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 4.5° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelson-ite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more pronounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,' the TiO2 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. Sampling Methods and Procedure During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this pos sible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1949

By D. M. Davidson

The drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company's standard core-drill outfits to complete 44 holes to an average depth of IIO ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered and is drained by the Piney and Tye Rivers, which are tributary to the James. Geology The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 4.5° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelson-ite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more pronounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,' the TiO2 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. Sampling Methods and Procedure During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this pos sible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1949

By Walter Lang

The year 1931 has shown a marked change over 1930 in New Mexico, with respect to the volume of activities attendant upon the petroleum industry. Although the total production of oil and gas this year exceeds that of preceding years, the results have been attained from established units operating under restriction, but capable of supplying far more than the economic conditions justify. The presidential order of March 12, 1929, that "there will be complete conservation of Government oil in this administration," has merely anticipated a normal consequence of overdevelopment. As a result of the combined economic and legal restrictions imposed, very little new drilling has occurred during the year. Even in proven areas the drilling of offsets has been curtailed to the absolute limit of requirements. Scouting and sample-cutting, which in 1930 were still in a state of feverish activity, are at low ebb, and lease buying has reached a condition of stagnation. A number of the major oil companies have either materially reduced their field and office forces or completely eliminated local office representation. Two tests of particular interest, because correlation shows them to be structurally high although they failed to produce, are the National Securities well drilled six miles west of the town of Hobbs, on sec. 33, T.18 S., R.37 E., Lea County, to a total depth of 4272 ft., which developed a flow of 4,000,000 cu. ft. of gas at 3860 ft., and a show of oil; and the Western Drilling Co. No. 1 State, sec. 16, T.20S., R.32 E., Lea County. The latter test found dead oil at 2575 to 2580 ft., and sulfur water at 2745 ft., increasing to 2780 ft., representing the zone from which production was generally expected. The well was drilled to 4013 feet. The discovery of sulfur at about 950 ft. in the deepening of an old water well (Pearson, NE. 1/4 sec. 8, T.16 S., R.25 E.) drilled in the Little Cottonwood area northwest of Artesia led the Union Sulphur Co. to drill three prospect tests on a block of acreage in the vicinity during the summer and fall. The results of the investigation have not been disclosed. The Kummbaca Oil and Gas Co. drilled the T. J. Kerline No. 1, in sec. 34, T.21 N., R.30 E., Harding County, gaging 3,654,000 cu. ft. of 98 per cent CO² at 940 ft. The Barton structure, 20 miles east of Albu-

Jan 1, 1932

By Zay Jeffries

A. G. WORTHING, Nela Park, Cleveland, Ohio (communication to the Secretary*).-The paper by Mr. Jeffries is very interesting. He is to be commended for his pioneer work in the study of equilibrium systems at the very high temperatures which one obtains with tungsten and molybdenum. There is one statement, however, to which I must take exception. On page 1227, a statement is made which would seem to indicate that the Nela Research Laboratory joined Dr. Langmuir in the recommendation of 3,300°C. as the most probable melting point of tungsten. This is not the case. In. the paper referred to by Mr. Jeffries, I have given 3,630°K. or 3,357°C. as the melting-point temperature for tungsten. Confirming observations by other workers in our laboratory justify the belief that this latter value is correct to within a small part of the discrepancy between the two values quoted.

Jan 12, 1916

ARIZONA Tucson University of AriZona, Mining Engineering Society. B CALIFORNIA Berkeley University of California, Mining Asso. B University of California, Library. B & T Los Angeles Chamber of Mines and Oil. B Southern California Local Section. T Public Library. B & T Oakland Oakland Free Library. T San Francisco California State Mining Bureau. T Mechanic's Merchantile Library. B Mining and Scientific Press. B Stanford University Stanford University Geological and Mining Society. B San Diego Public Library. B COLORADO Boulder University of Colorado, Library. T Denver Bureau of Mines. B Colorado Scientific Society. B Mining American. B Denver Public Library. B & T Golden Colorado School of Mines Magazine. B Colorado School of Mines Library. T Colorado School of Mines Scientific Society. B

Jan 1, 1923

By L. J. Buck

Lead smelting in the ore hearth, first practiced in Europe, whence the traditional name "Scotch hearth, and later developed in America to its present efficiency, is based upon the roast reduction process and is applicable to relatively high-grade galena concentrates. The roast reduction process embraces not only the roast reactions: 2PbS + 70 = PbO + PbSO4, + SO2 PbS + 2PbO = 3Pb + SO2 PbS + 2PbSO4 = Pb + 2PbO + 3SO2 but also, by reason of the addition of extraneous fuel, the reduction reaction: 2PbO + C = 2Pb + CO2 Thus in the ore hearth the roasting of lead sulphide, forming lead oxide and lead sulphate, the reaction of lead oxide and lead sulphate with lead sulphide producing lead, and the reduction of lead oxide by carbon producing lead, go on simultaneously. The Ore Hearth Function of the Ore Hearth.—The ore hearth, through the roast reduction process, provides for the extraction of lead and the immediate disposal of the smelting products—fume, hearth slag and lead, all of which are subsequently treated as follows: the fume is recovered in the flue system and baghouses, mixed with concentrates, and returned to the ore hearth in the form of ore mix; the hearth slag is smelted in a blast furnacc for the further recovery of lead; and the lead is refined and cast into a marketable product. Concentrates Amenable to Ore-hearth Smelting.—Only concentrates that are high in lead content, 70 per cent or more, are ordinarily considered amenable to ore-hearth smelting. Silica should not exceed 2 per cent and iron is allowable only to 4 per cent. These slag-forming constituents occlude both sulphide and mctallic lead, prevent the elimination of sulphur and decrease the lead extraction. Lime and magnesia are beneficial in that both favor a dry slag, promote elimination of sulphur, and prevent occlusions of metallic lead.

Jan 1, 1937

By D. F. Atkins, B. A. Rogers

The constitutional diagram presented herein is relatively simple. Complete mutual solid solubility exists for an interval below the solidus line, a continuous curve with a flat minimum near 22 pct Cb and 1740°C. Upon cooling, the solid solution breaks up, except at the columbium-rich side, from two causes: zirconium-rich alloys transform under the influence of the ß-a transformation in zirconium; alloys of intermediate composition decompose into two solid solutions below 1000°C. The combined effect is the formation of a eutectoid at a temperature of 610°C and a composition of 17.5 pct Cb. The eutectoid horizontal extends from 6.5 to 87.0 pct Cb. Some age hardening effects have been observed in the zirconium-rich alloys but the positions of the solvus lines remain uncertain. IN recent years, zirconium has been produced in much larger quantities than were available previously. Correspondingly, the incentive for studying its alloy systems has increased, as the number of recent publications on alloy systems testifies. However, only a partial diagram of the Zr-Cb system has been published and relatively few references have been made to alloys of the two metals. Hodge' investigated the Zr-Cb system up to about 25 pct Cb. His data on melting points were not sufficiently numerous to distinguish with certainty between the alternatives of a narrow eutec-tic horizontal and a wide flat minimum in the solidus curve. Although Hodge considered his results on transformations in the solid state to be only tentative, he suggested that the eutectoid in the zirconium-rich alloys lay at about 625 °C and 10 pct Cb and estimated that the solubility of colum-bium in zirconium at 625 °C was near 6 pct. According to Simcoe and Mudge,2 less than 0.5 pct Cb is soluble in zirconium at 800°C. These authors observed an increased strength in both the 0.5 and I pct Cb alloys made with hafnium-containing zirconium. According to Keeler,3 the strength of zirconium is increased by addition of columbium to a content of at least 3 pct. Keeler' also observed a maximum in hardness at about 10 atomic pct Cb and commented on the brittleness of alloys of this composition. Anderson, Hayes, Rober-son, and Kroll5 investigated the tensile properties of Zr-Cb alloys containing 5.1 and 12.9 pct Cb at room temperature and at 343°C. The 12.9 pct alloy had a high tensile strength at room temperature but also a low percentage of elongation. All alloys had high elongation at 343 °C. Littona measured strength and elongation values of annealed alloys containing up to 27.5 pct Cb and found low elongation values for all of the alloys of high columbium content. Some observations on the resistance of Zr-Cb alloys to corrosion in water at high temperature have been published by Lustman, De Paul, Glatter, and Thomas' who found that additions of columbium up to 1 pct had only a minor effect on the corrosion resistance of zirconium. Preparation of the Alloys Raw Material: Zirconium of a relatively good grade was available for making the alloys. It was obtained as scrap pieces that had been left over from an operation that included production by the iodide process, melting under a protecting atmosphere, and fabrication to plates. The individual pieces had hardness values of 24 to 32 Ra and a typical analysis is shown in Table I. The columbium also was scrap trimmed from sheets. It was furnished by the Fansteel Metallurgical Corp. and had a high ductility but its analysis was known only approximately. The metal probably contained about 0.5 pct Ta, perhaps 0.25 pct C, and a few hundredths percent each of iron, silicon, and titanium. Melting: The alloys were melted in a tungsten-electrode copper-crucible arc furnace similar to units that have been described recently in the metallurgical journals.'.' The crucible of this furnace is provided with a cavity in which a getter charge can be melted before the melting of the alloy charges. Hardness measurements on the ingots indicate that the getter charge takes up a considerable fraction of the oxygen and nitrogen from the helium atmosphere of the furnace. The alloys used in the investigation are given with their intended compositions, hardness, and melting points in Table 11. Fabrication: All alloys of the Zr-Cb system appear to be amenable to fabrication. At least, all of the compositions listed in Table II could be reduced to wires in a rotary swaging machine. The starting material was either slabs cut from ingots and ground by hand to rough cylinders or narrow strips trimmed from sheets made by cold rolling slabs. However, not all of the alloys could be fabricated satisfactorily by the same method. From 0 to 4 pct Cb and from 20 to 30 pct Cb or more, the alloys could be swaged cold from ¼ in. cylinders to 0.80 mm wires with only one intermediate annealing, sometimes with none. From 40 to 90 pct Cb, the alloys were difficult to swage either hot or cold but could

Jan 1, 1956

By N. J. Grant, A. W. Mullendore

Three aluminum alloys of 0.94, 1.92, and 5.10 pct Mg, prepared from very high purity metals, were tested at 500°, 700°, and 900°F in creep rupture. The degree of strengthening through solid-solu-tion alloying and the effects on the deformation characteristics and fracture were examined. The ductility of the alloys as a function of stress and temperature was closely followed. STUDIES of the creep process in pure metals in recent years have done much to expand the understanding of the fundamental deformation and recovery processes that contribute to overall creep behavior. In order that this knowledge may be applied to commercial alloys, it is necessary to know the principles governing the effect of alloying on the mechanisms of creep. A limited amount of work has been performed in this field, but few investigators have attempted to follow the changes in particular creep mechanisms with alloying. Recently, studies of the effects of solid-solution alloying on the plastic properties of aluminum have been conducted by Dorn, Pietrokowsky, and Tietz,1 Sherby, Anderson, and Dorn,2 and Sherby and Dorn.3 This paper presents the results of an investigation of the effect of solid-solution alloying of high purity aluminum with magnesium on the creep-rupture properties, and correlates these observations with changes in the creep mechanisms. This work is thus an extension of the creep-rupture observations of Servi and Grant4,5 and the deformation studies of Chang and Grant.6,7 Experimental Procedure Three alloys of aluminum containing approximately 1, 2, and 5 pct Mg were tested. These alloying additions are all within the solid-solubility limit at the testing temperatures.' The analysis of the materials is presented in Table I. The tests fall into two categories: l—creep-rup-ture tests at 500°, 700°, and 900°F, and 2—structure study tests performed primarily at 700°F. Speci-mens of 0.160 in. diameter with milled flats for metallographic observations" ' were utilized for the structure studies. All specimens were annealed in one step to give the desired grain size for the tests. Table II presents the annealing data and final grain sizes. The specimens were polished electrolytically before testing with Jacquet solution (2/3 acetic anhydride, 1/3 perchloric acid) at 25" to 30°C, and 15 to 20 v. Creep-rupture testing was performed under constant load with the apparatus previously described." Results and Discussion Creep-Rupture Properties: The log-log plots of creep-rupture data are presented in Figs. 1 and 2. For these very pure single-phase alloys, the minimum creep rate and the rupture life both exhibit straight-line dependence on stress in this method of plotting as they have for commercial alloys0,10 and for pure aluminum." Curve breaks, based on the use of straight-line segments, at 500°F have been found by metallographic study to correspond to a transition from low to high temperature behavior and so represent zones of equicohesion. Specimens on the high creep-rate side of the break showed normal granular deformation processes whereas those on the low creep-rate side showed rapidly increasing grain-boundary sliding and migration with extensive evidence of intercrystalline cracking at 500°F. Two micrographs of the 0.94 pct Mg alloy, Fig. 3, show the increased participation of the grain boundary in the deformation process at 500°F with decreasing stress. In Fig. 3a is shown the structure of a specimen which exhibits little deformation along the grain boundaries and failed transgranularly; in Fig. 3b is shown the increased deformation along the grain boundaries at a lower stress for a specimen which showed appreciable intercrystalline cracking. The severity of intercrystalline cracking increased with increasing magnesium content at 500°F. Intercrystalline cracking disappeared in most of the specimens at 700°F and persisted only in the 5 pct Mg alloy at high creep rates. At 900°F all of the specimens deformed with extensive grain-boundary participation, including extensive grain-boundary migration. None of the alloys at 900°F showed intercrystalline cracking.

Jan 1, 1955

By G. A. Beske, P. Hilsch, J. Wulff

The effects of the growth precipitates on the su-perconduching properties of an Al- 15 al. pel Zu alloy have been studied using magneization, transition lem-perature, and residual resistivity measurements. Aging at 230C for 1/2 to 11 he produces an increase in Hfp, Ike field of first penetration, and tut increase in trapped flux. The upper critical field, Hc2 remains constant for such aging tunes. Aging at 200°C produces a decrease in Hfp and an increase in trapped flux. The transition temperature remains constant at Tc - 1.227° ± 0.02°K for aging at 220°C for tims of from 1/2 to 10 hr, and for aging at 200°C it remains constant at Tc. = 1.18° i 0.02°K for times from 1/2 hv to 26 hr. The observed behavior indicates that the superconducting matrix when aged at 220°C behaves tike a type U su-perconducior, but when aged at 200°C behares like a type I superconductor. The magnetization changes after aging can be attributed to the growth and clutnge in distribution of the precipitate in a matrix of fixed composition. IT has been realized for some time that the superconducting properties of alloys are highly structure-sensitive. This is evident in the work of Mould and Mapother1 who examined the properties of an aluminum alloy. Precipitation effects have also been briefly mentioned in other studies.2-4 Bonnin and coworkers5 have observed a sharp inc rease in trapped flux in an A1-Mg alloy when the residual resistivity reaches a value that indicates it is a type II superconductor. Recently Blanc, Goodman, and Nemoz5p have reported on precipitation effects in A1-Ag alloys. Detailed studies of precipitation in Pb-Sn and Pb-Cd alloys made by Livingston6 serve to show that the upper critical fields are enhanced by quenched-in solute. Furthermore. at various stages in the precipitation process? the upper critical field is determined largely by the remanent solute. The observed magnetic hysteresis and trapped flux in such alloys result from the interaction between precipitate and the flux filaments in the mixed state. The flux trapping appears to depend largely on the precipitate distribution and is greater if the superconductor is type II than if it is type I. To examine the effect of precipitation in another alloy system, particularly one in which the composition of the superconducting phase does not change significantly during the course of precipitation, the Al-Zn system seems interesting, especially in view of the transition temperature and resistivity studies of Chiou and seraphim.' Furthermore, the recent detailed electron-microscope studies of an Al-Zn alloy by Richards and Garwood8 provide a guide for relating superconducting properties to changes in structure. For these reasons, magnetization, transition temperature, and residual resistivity measurements for varying times of heat treatment at two temperatures were made with a -15 at. pct Al-Zn alloy. The results are reported in this paper. I) EXPERIMENTAL The alloy used was prepared by Cominco Products Inc. from 99.9999 A1 and 99.999 Zn. It was chill-cast, swaged, and drawn to 0.125-in.-diam rod. The analyzed composition was 15.6 at. pct Zn (31.1 wt pct). A jeweler's saw was used to cut the 0.125-in.-diam rod into the 0.875-in. lengths needed for magnetization measurements. The ends of the cylinders were slightly beveled to remove the sharp edges. A portion of the original 0.125-in.-diam rod was drawn into 0.010-in.-diam wire and used for transition temperature measurements. Specimens were suspended from wires within a vertical furnace during heat treatment. All were homogenized at 500°C for a minimum of 3 days and subsequently solutionized for times in excess of 6 hr. The solutionizing temperature was held constant to +3°C. Individual specimens were homogenized, quenched, and aged several times and no effects indicating loss of zinc were noted. The suspended specimens were quenched by cutting the wires and allowing the specimens to fall into a silicone oil bath held at the aging temperature. They were then isothermally transforked by aging in the same bath used for quenching. After aging for the required time (approximately 10 min aging was necessary before the upper critical field reached a fixed value), they were briefly (1 to 2 sec) dipped into an acetone bath at room temperature to remove adherent oil and then immediately transferred to liquid nitrogen where they remained until inserted into the helium bath (usually within an hour). The temperature of the aging bath was held constant to +3°C for longer aging times. The cryostat used for the measurement of superconducting properties consisted of outer and inner dewars for liquid nitrogen and liquid helium, Stokes 6-in. booster diffusion pump and Stokes Model 212 mechanical pump, temperature controller to measure and control the temperature of the helium bath, and a superconducting solenoid with inserted search coils to provide the magnetic field and measure the magnetic moment of the specimens. A schematic diagram of the cryostat is shown in Fig. 1. An ultimate temperature of 0.85°K was reached with this apparatus. The temperature controller used is similar to the one described by Blake and chase.' A 0.5 pct Allen-Bradley carbon resistor and a nichronle heater (200

Jan 1, 1968

By A Andersen

DURING an investigation of the copper-rich portion of the copper-silicon-iron system as part of an extensive research program on P.M.G. alloys, which was begun in 1937 in the research laboratory of the Phelps Dodge Corporation, it became apparent that the binary copper-silicon system below 7 per cent Si needed revision, therefore an investiga-tion was undertaken. Both X-ray methods and microscopic technique were employed. Despite the many investigations that have the clarification of this sys-tem as their object, no two successive reports on the system have agreed in placement of the alpha-phase solubility limit, and uncertainty about the secondary phase first to appear has been voiced several times.3,4,5 It was therefore not surprising, when T. Isawa's6 and M. Okamoto's7 works were reported at the time we were finishing up our experimental work, to find essential disagreement between their results and ours. But when C. S. Smith's latest work on the copper-silicon system8 was published just as we were finishing our laboratory report, it was indeed gratifying to find that the latter's diagram and ours checked in all essen-tial features, except the temperature of the peritectic line above 830° C. Many attempts were made to retain the beta phase during the present investigation, but none was successful. Isawa,6 however, reports that he has been able to obtain X-ray photograms of the beta phase. The structure, he states, is body-centered cubic with a lattice constant of 2.848 A.. at 7.2 per cent Si. Okamoto7 and Smith8 both use the designation Kappa for the hexag-onal phase, and to avoid confusion this designation will be adhered to in the present paper.

Jan 1, 1939

By John B. Dilworth

In September, 1930, H. N. Eavenson, then Chairman of the Coal Division, appointed a Committee on Methods of valuing Coal Propelvties, with John B. Dilworth as chairman. The latter prepared a schedule' of features for consideration under the general headings of Undeveloped and Developed Coal Properties. These subjects were divided among the members of the committee and during the next year written discussions of his allotted subjects were received from each member. Mr. Grimes and Mr. Eavenson discussed the entire list,. These discussions were mimeographed and a set sent to each member before the meeting of the Institute in February, 1932. There was a general discussion at that meeting. At the meeting in February, 1934, Mr. Dilworth submitted a report12 which summarized the accumulated opinions and data and presented the conclusions of the committee as a whole on the subjects embraced in it's schedule. Members of the committee expressed the desire that some of the individual opinions be published for reference. Mr. R. Damon Hall's abstracts of these papers arc therefore presentrd herewith.3 Personnel of Committee John B. Dilworth (Chairman), Consulting Mining Engineer, Edward V. D'Invilliers Engineering Co., Philadelphia, Pa. Eli T. Conner, Consulting Mining Engineer, Seranton, Pa. W. G. Duncan, Jr., Superintendent, W. G. Duncan CoaI Co., Greenville, Ky. Howard N. EAveNson, Consulting Mining Engineer; Eavenson, Alford & Hicks. Pittshurgh, Pa. George Watkin Evans, Consulting Mining Engineer, Seattle, Wash. J. A. Garcia, Consulting And Constructing Engineer, Allen & Garcia Co., Chicatgo. III. John Alden Grimes, Valuation Engineer, Bureau of Internal Revenue, Washington, D. C. Otto Herres, Assistant Manager, United States Fue1 Co., Salt Lake City, Utah. J. R. Hicks, Consulting Mining Engineer, Eavensorl, Alford & Hicks, Pittsburgh, Pa. Robert D. Reeder, Mining Engineer, U. S. Bureau of Mines, Washington, D. C. Samuel, A. Taylor, Consulting Engineer, Pittsburgh, Pa. Bleeckee L.. WHeeler, Mining Engineer, Ford, Bacon & Davis, New York, N. Y.

Jan 1, 1934

By J. W. Stewart

THE aim of this paper is to point out the various ways in which design is taught in standard four-year mining engineering curricula in American colleges and universities; to discuss the reasons apparently justifying the great diversity of procedure that exists along this line; and to indicate possible solutions to the difficulties now attending the teaching of design. A study was made of typical four-year mining engineering curricula in 15 colleges and universities of the United States (Table I). Great diversity in content of the various design courses, if taught as described, became apparent immediately. It appeared that it might be both interesting and instructive if the cause for this colorful variety could be found. Was the cause local mining conditions, departmental individuality, or actual necessity? Study of the school catalogues revealed that the various design courses could be classified into two fairly distinct types; namely, (I) those dealing with mine equipment or structures, and (2) those dealing with underground layout of mine workings. It seemed reasonable to label the first type of course "mining design" and the second type "mine design." Some such distinction must have been in the minds of mining educators, for we find both names (i.e., mine design and mining design) used to designate the design courses included in the various mining curricula. Unhappily, the name and the apparent content of such courses do not, in all instances, conform to the classification made here, although in most instances such conformation does obtain (Table I), It is possible that in the exceptional case the method of teaching a design course, and consequently the content of it, may have been changed at some time without change in the name of the course. Apparently only 3 of the I5 schools made an effort to cover both types of design in their curricula (Table I). Two other schools did not list or describe any course of study that could with certainty be taken as a design course. Of the remaining 10 schools, 9 gave a mining-design type of course and one gave a strictly mine-design type. Obviously, the preponderance of design courses afforded are of the mining-design type. Why? To answer this question, it is necessary to make a study of the prerequisites for the two types of design courses taught. In all schools the design courses were taught in the senior year; in eight, design was taught throughout both semesters; in two, it was taught during the first semester only; and in three it was taught during the second semester only. Consequently, excepting the last three cases noted, it is obvious that all prerequisites for a design course should be completed by the end of the junior year. PREREQUISITES What are the probable prerequisites for the different kinds of design courses as they appear to be taught? Let us take first the case of the mine-design type of course, having to do with layout of underground workings. Here it would seem that logical

Jan 1, 1941

By O. J. C. Runnalls, L. M. Pidgeon

J. M. Blocher, Jr. and I. E. Campbell (Battelle Memorial Institute, Columbus, Ohio)—Since the de Boer-Van Arkel process for making titanium metal involves a number of steps in a fairly compact unit, it is difficult to determine simply which of the steps is rate controlling. In any statement as to which step constitutes the rate-controlling process, qualifications appear to be in order. It is possible to design a reaction bulb in which any one of a number of steps is made to be controlling. I—With the filament removed some distance from the crude, as in the case of the authors' experiments, the interdiffusion of iodine and iodide may be controlling. 2—If, as is usually done, the crude metal is placed in a perforated cylindrical basket, or as a briquetted mass, in close proximity to the filament, the rate of deposition is increased (we obtained rates of deposition 5 to 10 times those cited in the authors' paper), and another rate-limiting factor, such as the reactivity of the crude, may take over. In this regard, we have noticed radically different rates of deposition with different crudes, and with crudes in various stages of exhaustion. 3—With a very reactive crude metal and with optimum practical geometry, still another process may be controlling. It is felt that this is a diffusion process in the immediate vicinity of the filament involving the fundamentally adverse situation of a net flow of particles away from the filament. The separate experiments on the reactivity of iodine with titanium are interesting but somewhat inconclusive. Data is still needed on the partial pressure of iodine in an operating decomposition bulb. A knowledge of the gradient of iodine partial pressure from the crude to the filament would be particularly enlightening. Optical absorption may be a useful technique here. Accurate measurements of the total pressure within a decomposition bulb under various conditions would be quite revealing. Preliminary measurements have been made at Battelle in following this line of attack. It is interesting to note that the authors' data on the temperature dependence of deposition rate indicate that the overall rate is not controlled by the kinetics of the decomposition reaction at the filament: TiI1 ? Ti + 4I Any reasonable estimate of the activation energy of this reaction would, if its kinetics were controlling, dictate a much greater temperature dependence than is observed here. The authors apparently attribute the drop in deposition rate (eventually to zero) with increased TiI4 pressure solely to a decrease in diffusion rate. However, there is an equilibrium factor involved here that must not be overlooked. As the partial pressure of TiI4 is increased, a point is reached where, due to the competing reaction of the tetraiodide with titanium to form lower iodides, the equilibrium partial pressure of titanium is reduced to the point that it equals the vapor pressure of titanium at the filament temperature and the deposition rate falls to zero. This effect would

Jan 1, 1953

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By AIME AIME

WHEN I was getting data for my books on ore dressing, I traveled across the continent, visiting a great many mills, always accompanied by my vanning shovel, and I got to be a joke among the millmen. They would say "Here comes the Professor with his vanning shovel." With the aid of this vanning shovel, I examined the tailings of all the mills I visited and I found it to be universally true that they contained some extremely fine, free mineral. I looked everywhere to see if I could find a machine or a process that would save this fine mineral. But nowhere did I find anything that made any bid for success until I visited the Kennedy mill, with its Gates canvas plant, on the Mother Lode of California. There I found that the tailings of the Frue vanners were put into a one-spigot classifier of good design which yielded a spigot product entirely free from this fine, free mineral which only assayed 40c. to the ton in gold. The overflow was extremely fine and as¬sayed $3 to the ton. This overflow was fed to ten canvas tables each 10 ft. square, with the grain of the canvas running across the table to make for the roughest surface. The canvas used was No. 6 cotton duck sail cloth.

Jan 1, 1934