Search Documents

By Knut L. Sandvik, Aage Solbakken

it is an established fact that the collecting properties of xanthates and anionic collectors are dependent on the hydrocarbon chain length. This is ascribed to the greater adsorption densities caused by increasing the xanthate chain length. As batch flotation tests showed similar trends for amines, an investigation of the adsorbing properties of amines was undertaken. Because earlier investigations showed adsorption densities for dodecylamine salts on quartz varying as much as 20 times under apparently similar conditions,1-4 it was decided to make a survey of the changes in adsorption density due to the drying conditions of the quartz. EXPERIMENTAL PROCEDURE The quartz, handpicked in the pegmatite quarries of Iveland, Setesdal, had the following composition: SiO2 99.81, A12O3 0.01, Fe2O3 0.05 and loss by ig-

Jan 1, 1969

Canada's newest low-grade porphyry copper mine, Gibralter Mines Ltd. (N.P.L.), has reached production. The subsidiary of Placer Development Ltd., located at Williams Lake in the Caraboo District of central British Columbia, began open pit mining in mid-June on reserves estimated at 358 million tons assaying 0.373r: Cu and 0.016C; MoS,. Each of four separate zones will be mined in a predetermined sequence, in one or more stages, and with a throughput of more than 36,000 tpd. The sequence and stages of mining the zones have been determined by computer calculation and economic analysis and are designed to maximize recovery and minimize cost. At the very least, the mine is off to a promising start. Development costs leveled off at $67 million. 9'; below the anticipated budget.

Jan 7, 1972

By J. M. Dupouy, R. A. Rawe, M. B. Bever

The aging characteristics of a titanium alloy containing 13 pct V, I1 pct Cr, and 4 pct A1 have been investigated by hardness measurements, X-ray diffraction, and metallography. The P phase decomposes into 0 + a, and 0 + a, + TiCr, above about 1050°F; below this temperature a transition phase, believed to be w, precipitates first, followed by a, and TiCr,. The observed hardening is attributed to these reactions. Cold working of solution-treated specimens accelerates hardening and raises the hardness level attained. A TTT diagram is proposed. NEW titanium-base alloys, designated as "all-beta," have recently been developed. These alloys contain large amounts of P-stabilizing elements such as molybdenum, chromium, or vanadium. When cooled from the solution temperature, they consist only of P; in particular, the martensitic a,' phase does not form.

Jan 1, 1961

By S. Yukawa, M. J. Sinott

The low solubility of bismuth in copper and its segregation at copper grain boundaries with resulting embrittlement is well known.1-3 The heterogeneous diffusion of liquid bismuth into polycrystalline copper has also been studied.4 This work presents some further observations on these phenomena using high-resolution auto radiography to detect the presence of bismuth in copper polycrystalline and bicrystal specimens. The auto radiographs were made by the stripping film technique which produces an autoradiograph that is intact with specimen surface and can be examined simultaneously with the under-lying microstructure. The details of the technique have been described previously.3 In one series of experiments, high-purity copper was alloyed with 0.02 to 0.03 wt pct radioactive bismuth obtained from the Oak Ridge National Laboratory. Melting and casting was done under a

Jan 1, 1960

By C. Feng, C. Elbaum

AN investigation of the fracture plane of titanium, containing 0.5 wt pct to 1 wt pct 0, was recently carried out by fracturing large-grain specimens in a tensile jig at room and liquid air temperature. The experiments were carried out on strip specimens 3 to 5 mm wide, 2 mm thick and about 100 mm long. The specimens consisted of several grains, each occupying the entire cross section of the strip and extending over a length varying from 5 to 20 mm. These specimens were prepared by a method described elsewhere.' The identification of the fracture plane was possible in twelve of approximately thirty crystals investigated. In some cases severe local distortion took place near the fracture and prevented identification of the fracture plane. On, at least, three occasions the fracture propagated in a helicoidal

Jan 1, 1959

By André G. Journel

Geological study of the Prony Nilaterite (New Caledonia) began in 1969 and included drilling, geological mapping and laboratory studies. The deposit is the product of weathering of basic rocks. From top to bottom, the following zones can be distinguished: a compact ferruginous cover; ore associated with yellow laterite, containing 1.0-1.5% Ni and low in impurities (SiO2, Mg); an intermediate silicated ore containing 1.3-2.0% Ni and higher percentages of impurities; garnierite ore much richer in nickel (2-4%) but high in SiO, and Mg contents (Mg up to 20%) ; and parent rock, largely peridotites. Distinction between types of ore is essential because the high grade ore (silicated and granierites) is penalized for its high Mg contents that demand additional acid treatment. All studies made distinguish two types of ore, laterite and silicated.

Jan 10, 1973

Weston Portable Electrodynamometer The Weston Electrical Instrument Co. of Newark, N. J., believes that problems hitherto considered impossible of solution in the designing of portable electrodynamometers have been solved in its new models. The voltmeter, Model 341, is an instrument' of precision adapted to use on alterating- or direct-current circuits, guaranteed to an accuracy of 0.25 per cent. full-scale value either on direct or alternating-current circuits of any frequency to 133 cycles per second and commercial frequencies even as high as 500 cycles per second with very slight error. The polyphase electrodynamometer, Model 329, is accurate to 0.5 per cent. under the same conditions.; Double ranges are furnished in all instruments of this model. All current ranges can be used for 100 per cent. overload indefinitely without introducing error in Models 310 and 329.

Jan 12, 1915

The following officers and committee chairmen were elected: Honorary Chairman, Herbert Hoover; Chairman, Elmer A. Sperry, New York; Vice-Chairman and Chair-man of the Executive Committee, John W. Lieb, New York; Vice-Chairman, C. E. Grunsky (Pacific Coast), San Francisco; C. F. Kettering (Middle West), Detroit; Execu-tive Secretary, Maurice Holland; Executive Committee: Gano Dunn, George W. Fuller, Maurice Holland, Frank B. Jewett, John W. Lieb, H. J. McGraw, Calvin W. Rice, W. E. Wickenden, all of New York; Dugald C. Jackson, Cambridge, Mass.; 0. C. Merrill, Washington, D. C.; Charles F. Scott, New Haven, Conn.; Elmer A. Sperry, Brooklyn, N. Y.; Finance Committee. John W. Lieb; Technical Program Committee: D. C. Jackson; Transporta-tion Committee: F. B. Jewett; Entertainment Committee: 0. C. Merrill; Publicity: J. H. McGraw; Promotion and Attendance: George W. Fuller.

Jan 5, 1928

By R. S. Goodrich, G. S. Ansell

The microstructure of three Al-Al2O3 SAP-Type alloys (containing 2.0, 3.0, and 5.7 wt pct alumina, respectively) was studied utilizing transmission electron microscopy. These alloys were fabricated from aluminum powders by powder-metallurgical techniques, cold-rolled into thin strips, and recrys -tallized. Thin foils suitable for an electron-transmission study were then prepared from the strip material by electropolishing. The microstructure of these alloys is shown to consist of small (0.1 mean diameter) plate -shaped alumina particles finely distributed in an aluminum matrix. In the higher-oxide content alloys the platelets are somewhat larger and more irregular in shape. The distribution of oxide particles is not uniform and there is an increasing tendency toward clumping SINCE the discovery by Irmann1 that aluminum alloys produced by compacting, hot pressing, and extruding fine aluminum powders possess remarkable high-temperature mechanical properties, the Al-A12O3 SAP-Type alloys have been utilized extensively as model dispersion-strengthened alloys in both experimental and theoretical invest igations.2-8 The use of the SAP-Type alloys as model dispersion-strengthened alloys implicitly assumes that their microstructure has been completely delineated. This is, however, not the case. with increasing oxide content. In all the alloys studied, the mean center-to-center spacing of particles was quite small (0.2 u) due to the very fine oxide debris present. Selected-area diffraction of the specimen identified the oxide as either y Al2O3 or y' Al2o3. The re crystallized MD-5100 alloy exhibited a mean grain diameter of only 0.7u, while the grain size of the other alloys was several hundred microns. Severe pinning of the grain boundaries by oxide particles was rarely observed, and the grain boundary triple points in the small-grained MD-5100 alloy were often particle -free. Diffraction contrasts visible around the particles are attributed to elastic strain fields set up by differential thermal contraction during cooling from the recrystallization anneal. Early investigation demonstrated that optical metallography did not possess sufficient resolution to observe the microstructure of the SAP-Type alloys.' Later, extensive use was made of replication techniques to study the microstructure by means of electron microscopy.7-9 These studies indicated that the SAP-Type alloys consist of a dispertion of irregular Al2O3 platelets, approximately 150A thick 9 and a micron or so on edge,9 distributed in a matrix of commercial-purity aluminum. These oxide platelets tend to be oriented in the aluminum matrix, with their largest dimension parallel to the extrusion direction. 8,9 A study employing polarized-light techniques1' indicated that the grain size of a series of as-extruded SAP-Type alloys was several microns in diameter, while the grain size after re-crystallization was several millimeters in diameter. A more recent study 12 utilizing surface-replication techniques examined the particle morphology,

Jan 1, 1964

IN the early period of steelmaking, ingot structure and segregation were of no practical importance. Crucible melting required very small ingots that gave little segregation, and a small inserted hot top prevented pipe. As larger ingots were poured from bessemer converters and open-hearth furnaces, segrega- [ ] tion, piping, and gas evolution became increasingly important. The techniques of making semikilled and rimmed ingots were developed with little knowledge of the actual mechanism of the process. The first studies of solidification were made by the Brearleys1 and Gathmann,2- who used stearine to show the effects of shrinkage and mold shape. Fig 11-1 is a picture of a series of stearine ingots at various stages of solidification. These studies showed that the liquid solidifies at a nearly uniform rate from the sides and bottom of the mold and demonstrated the formation of

Jan 1, 1964

By Zay Jeffries

EACH generation accepts the developments of the preceding generations without full appreciation of the difficulties that had to be overcome or of the effect of any given development on society. Today, the production of pig iron is the yardstick with which general industrial health and progress are measured. So natural and logical does this seem to us, that it is difficult to picture conditions prior to the fourteenth century when pig iron was unknown. Not only was pig iron unknown but iron or steel could not be melted and poured into castings; all iron and steel articles were forged from sponge iron. All castings, as well as many worked articles, were made of non-ferrous metals or alloys. In many parts of the world, over long periods of time, not only was the annual exchange value of non-ferrous metals greater than that of iron and steel, but their combined tonnage was greater. At present, the value of the pig iron produced in a year is of the same order of magnitude as that of all non-ferrous metals combined; the tonnage of pig iron is, however, about twenty times that of all non-ferrous metals combined. Owing to lack of records, we will probably never know the relative importance of the various metals at all periods in historic times. A certain conclusion is that the iron and steel industry, since the discovery of pig iron and the cheap methods of converting it into steel, has grown at a much more rapid rate than the non-ferrous metal industries. Notwith-standing their fundamental fitness for man's needs, iron and steel owe their importance in no small degree to the low cost of production. The low cost was a result of increased knowledge of the production appliances and of the metallurgical processes. This increased knowledge is the key to our modern industrial civilization.

Jan 5, 1924

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By Joseph Hyde Pratt, Douglas B. Sterrett

Monazite is one of the minerals which, for a long time, was considered somewhat rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas arid Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals,ceriunl, lanthanum, and didymium,(Ce,La,Di)PO,. There is nearly always present a varying but small percentage of thoria, Tho2, and silicic acid, SiO2,, which are very probably united in the form of a thorium silicate, ThSiO4. Some mona-zites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent.; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellop. in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a con-choidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that werc 6 in. in length. The more perfect crystals are,-however,

Jan 1, 1910

By E. F. Koch, J. L. Walter

oriented crystals of iron and iron with 3, 5, and 6.25 pct Si were rolled to reductions of 10 and 70 to 97 pct at room temperature. Similarly oriented crystals were deformed in tension. Dislocation substructures of the deformed crystals were observed by transmission electron microscopy to determine the effect of silicon on the formation of substructures. Pole figures were obtained to relate orientation changes to substructure. When rolled 10 pct, the iron crystals and the 3 pct Si-Fe crystals formed cells, 1 and 0.2 u in diameter, respecliuely. Cells were absent in the higher-silicon crystals. Extended dislocations and possible stacking faults were observed in the 6.25 pct Si-Fe crystal rolled 10 pct and annealed at 650°C. The stacking-fault energy was estimated to be 20 ergs per sq cm. Rolling to 70 pct resulted in the formation of sub-bands (0.9 µ wide) ill the iron crystals and transition bands (containing 0.2-µ-wide subbands) in the 3 pct Si crystals. No subbands formed in the 5 pct Si-Fe crystal until it was ankzealed. SliP occurred on (112) planes ill tension. The slip traces on the 3 pct Si crystal were wary while those on the 5 pct Si crystal wvere straight. The strain-hardening coefficient for the 5 pct Si crystal was nearly zero. Cells did not form, at least at elongations up to 10 pet. The results suggest that cross slip of iron is restricted by additions of silicon beyond about 3 pct possibly by formation of immobile extended dislocations. IN a previous paper' the authors described the substructures developed in (100)[001]-oriented crystals of 3 pct Si-Fe which were rolled to reductions of 10 to 90 pct at room temperature. At low reductions (10 to 20 pct) cells, approximately 0.2 to 0.3 ja in diameter, were formed. The cell walls consisted mainly of edge dislocations. With increasing reduction (up to 50 pct) the cells were seen to elongate in the rolling direction. In certain regions of the crystal there were significant reorientations which were characterized as rotations about an axis normal to the (100) or rolling plane. These regions were called "transition bands". The regions in which there were no reorientations were called ('deformation bands". At reductions of 60 to 70 pct the elongated cells in the transition bands became sub-bands separated by low-angle tilt boundaries with angles of disorientation of about 2 deg. The elongated cell structure in the deformation band was replaced by a general distribution of dislocations. It was noted that the width of the subbands in the transition bands remained 0.2 to 0.3 µ; i .e., the width of the subbands was the same as the initial cell diameter for reductions up to at least 70 pct. From this, and from considerations of the mechanism of formation of the transition bands,' it was concluded that the subbands evolved directly from the initial cells. In order to check this conclusion, it was decided to examine the relationship between initial cell diameter and width of subbands produced by large rolling reductions. Cell size is known to be dependent upon the temperature of deformation.2,3 However, preliminary experiments with 3 pct Si-Fe crystals indicated that the change in cell size with increasing temperature of deform,ation was not sufficient for the present purpose. On the other hand, cell diameters generally reported for iron deformed at room temperature2'3 range from 1 to 2 p, a factor of 3 to 10 larger than the cells in 3 pct Si-Fe rolled to 10 pct reduction,' indicating the possibility of a marked dependence of substructure (at least in terms of cell size) on the amount of silicon in iron. Thus, the investigation was enlarged to include the study of the effects of varying silicon content on substructure in lightly rolled as well as in heavily rolled crystals of iron and iron with 3, 5, and 6.25 pct Si. The crystals used in this study all had the same orientation, (100)[001], with respect to rolling plane and rolling direction. These were rolled to reductions of from 10 to 97 pct and the substructures determined by electron transmission microscopy in both the rolled state and after annealing. In addition, stress-strain curves were obtained from (100)[001]-oriented crystals of iron and 3 and 5 pct Si-Fe to determine the effect of silicon on tensile properties. The dislocation substructure of the tensile specimens was also determined for Samples pulled to 2 and 10 pct elongation at room temperature for comparison with the substructures produced by rolling. 1) EXPERIMENTAL PROCEDURE Crystals with 3, 5, and 6.25 pct Si were prepared by annealing 0.012-in.-thick sheets of high-purity Si-Fe in purified argon at 1200°C to effect growth

Jan 1, 1965

By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01' "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,' and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl' at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.''' The oxygen pressures of "(Fe,Mn)07' solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l' The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.'2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07' solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By B. L. Averbach, M. F. Comerford, M. B. Rough

The volume fraction of ß phase was determined in a Ti-6Al-4V alloy by measurements of integrated diffraction intensities. The (0002), and (100)ß diffraction lines were chosen because this combination minimizes the errors resulting from preferred orientation. The difficulties arising from fluorescence radiation were eliminated by use of a diffracted beam monochromator. A specimen quenched from 1475OF (800°C) contained approximately 5 pct ß, but in specimens quenched from higher temperatures no ß was found. The ß phase formed during aging, and in specimens solution treated at 1570oF (855oC) approximately 10 pct ß was present after aging at 1000°F (540°C) for 24 hr. This ß appears to form by decomposition of martensitic a'. ThE kinetics of the reactions which occur during the heat treatment of titanium alloys are complex ' and not completely understood. It has been proposed that hardening occurs in some alloys' on aging by the precipitation of a transition phase w followed by the formation of the stable a and ß phases. It has been proposed for other alloys2 that the a' marten-site decomposes by precipitating finely dispersed a particles. Most investigations have been hampered by the difficulties of determining quantitatively the amounts of the various phases present. This paper is concerned with the measurement of the amount of ß phase by an X-ray method, similar to one developed for the determination of retained austenite. The principal new feature was the use of a mono-chromator in the diffracted beam in order to reduce the fluorescence arising from the sample. EXPERIMENTAL PROCEDURE The experiments were carried out on an alloy of nominal composition Ti-6Al-4V (actual weight percentages: 6.2 Al, 4.1 V, 0.02 Mn, 0.17 Fe, 0.005 H, 0.03 C, and 0.02 N). The material was received as 5/8-in.-diam centerless ground rods in the annealed condition. The heat treatments were carried out in a vacuum of approximately 0.03µHg. The X-ray intensity measurements were made on 3/8-in. thick discs. The surface was prepared by grinding off about 0.060 in. and electropolishing in a solution af 60 ml (70 to 72 pct) perchloric acid in 1000 ml glacial acetic acid with a current density of 0.5 amp per sq cm.q The X-ray determination is based on the proportionality of the diffracted intensity of each line to the volume fraction of the corresponding phase. In calculating the intensities for a powder sample it is assumed that a large number of grains con- tributes to the diffracted intensity and that the grains are oriented at random. The presence of preferred orientation introduces serious errors in the relative intensities. The material used in this investigation exhibited a strong preferred orientation, which could not be removed by heat treatment. Other investigators have also found that preferred orientation may be retained after phase transformations. Glen and pugh5 performed a detailed analysis of the randomness expected after several allotropic transformations, but stated that this is not observed. Burgers,6 and Burgers and Ploos van Amstel,7 found that, in zirconium, the original orientation is retained after two phase transformations. Newkirk and Geisler8 observed similar behavior in titanium. On the basis of this evidence, it appears that, in the absence of plastic deformation, textures present in annealed titanium alloys are retained. Heating an a-ß alloy to the all-ß region and subsequent cooling to room temperature do not make the orientation of the mar-tensite different from that of the original a phase. In the present investigation it was possible to take advantage of the crystallographic relationships involved in the martensitic transformation to minimize the errors associated with preferred orientation. The relative orientation for titaniu-m marten-site9 takes the form (0001), 11 (110)ß; [1120], 11 [lll]ß. The same relationship has been proposed for zirconium' and certain titanium-base alloys.10-12 Additional sets of approximately parallel planes have been determined for titanium-nickel alloys." The influence of preferred orientation can be minimized by comparing intensities from parallel planes in the two related phases. If it is assumed that each family of planes in a given phase is equally well populated, the effect of preferred orientation can be eliminated by using the normal multiplicity for the family of planes since each set of parallel planes is equally preferred for any orientation of the sample relative to the X-ray beam. The most suitable combination of reflections in the Ti-6A1-4V alloy appeared to be (0002), and (110)ß It must be recognized that the ß formed during aging of the Ti-6A1-4V alloy is a precipitate rather

Jan 1, 1960

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony' states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate of oxidation of ferrous iron to ferric iron in pure molten iron oxide by carbon dioxide + carbon moloxide mixtures at 1550°C. It is shown that the rate-controlling process is the interdiffusion of iron and oxygen atoms within the melt. The inter-diffusivity of iron and oxygen in the melt is obtained from the results and the value of (5.0 * 1.0) x 10-5sq cm per sec is recommended for the temperature of 1550°C. Similarly, it is also found that the rate of reduction of molten iron oxide is con -trolled by diffusion in the melt; however, apparent interdiffusivity values from these experiments are 10 to 20 pct higher than those obtained in the oxidation experiments, by virtue of convection arising from density difference. The results of the oxidation experintents are used to calculate an estimated self-diffusivity of iron in molten iron oxide of (1.5 * 0.5) x sq cm per sec. BECAUSE of the industrial importance of iron oxides, the study of the kinetics of both the reduction and oxidation of the solid oxides has received a great deal of attention. However, knowledge of the kinetics of similar reactions in the liquid state is very meager. Dancy 1 studied the kinetics of reduction of molten iron oxide by carbon in pig iron and found that the reaction is very fast. It was concluded from the results that the reduction of molten ferrous oxide is a first-order reaction up to 80 pct reduction, while

Jan 1, 1964

By C. A. Heberlein

C. A. HEBERLEIN, New York, N. Y.-The results stated by Rey and Brevers are so startling that they are of great interest, as the concentration of a low percentage of cinnabar by differential flotation yields a high-grade concentrate in the presence of either arsenical or iron pyrite. The authors say: "Cyanide can thus be used to depress arsenopyrite and make a good cinnabar-arsenopyrite separation. A cinnabar-pyrite separation could probably be effected in the same way." Corrosive sublimate at the present price of mercury would be a very expensive reagent but the expense would be justifiable if a high rate of concentration could be obtained with a high extraction. On my request, special tests were made in the Punitaqui mill in Chile along the line suggested by the authors, without any improvement of either grade or extraction. As the recovery of the cinnabar in a complex sulphide of chalcopyrite and pyrite gave unsatisfactory results, I had tests made at the testing laboratory of the American Cyanamid Co. at Stamford, Conn. As these tests turned out to be highly satisfactory, not only at Stamford but later at the mine, they are presented here. [ ] The pulp had a density of 22 and a pH of 7.8. Total time of conditioning was one minute. The reagent added was Texas fuel oil, 0.116lb. of 33.7 Bé. gravity containing 0.9 per cent sulphur. Frother, 0.062 lb. of No. 5 pine oil. Rate of concentration of mercury was 25.7: 11. [ ]

Jan 1, 1941

By W. E. Bron, E. S. Machlin

GRAIN boundary migration in V-shaped thin specimens of high purity silver was studied. Each specimen contained two crystals having the relative orientation: (111)A/(111)B; (ll0)A/(101)B. The boundary between these two crystals varied between a continuous curved and an alternating two plane interface. The plane interfaces were oriented parallel to (101)A/(011B) and (121)A/(211)B. Traces of these planes are shown in Fig. 1. Evidently the two plane interface, although of higher area, comprises lower total interface energy than the average curved boundary it replaced. The plane boundaries were found to move at 650 °C to consume the broad segment of the V opposite to the direction of interface area and energy decrease. On investigation, using the thermal etching technique of Hendrickson and Machlin,1 it was found that the outer grain contained 8.3x108 more dislocations per cm" than the grain at the apex of the V. Consequently, the boundary moved to decrease the strain energy associated with the difference in dislocation density across the boundary. The rates of motion of specific {110} and {112} boundaries were measured during interrupted anneals at 650°C by referring the position of the boundaries to each other and a fiducial line on the specimen surface. The measured rates of motion are 0.075 and 0.025 mm per hr for the {110} and {112} boundaries, respectively. Plots of grain boundary motion vs time of annealing show straight lines with little deviation of data points from these lines.

Jan 1, 1957