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By N. A. Gokcen, M. N. Dastur

In metallurgical process industries a knowledge of true melting and casting temperatures is very essential for increasing the operating efficiency as well as improving the quality of the finished product. Optical pyrometers are widely used for the purpose because of their cheapness and ease of operation. It is an unfortunate fact, however, that this mode of measuring temperature entails a source of severe error inasmuch as with all non-black bodies, the temperature observed is always below the true temperature owing to deficient emissive power. Hence, the need for emissivity correction arises. In 1913 Bidwell1 obtained emissivity values of 0.36-0.48 for a temperature range of 1520-1800°C. He measured the true temperature of molten iron by sighting into a carbon cavity immersed in the iron under an atmosphere of hydrogen. In 1914 Burgess2 determined the emissivity of a smooth surface of liquid iron free from oxide to be 0.37 under an atmosphere of hydrogen. He claimed to have attained an accuracy of within 5°C at 1500°C with an optical pyrometer using monochromatic light. He reported that no difference appeared to exist between the emissivities of pure iron and of steels containing considerable percentages of carbon, nickel or manganese; nor was there any appreciable variation of emissivity with temperature from 1530 to 1571°C. Wensel and Roeser3 found an elnissivity value of 0.4 for temperatures above 1375°C for cast iron. The average emissivity value for carbon steels reported by Leiber,4 odd,5 Hase6 and Umino7 range from 0.4 to 0.45. Knowles and Sarjant8 made an extensive study of emissivity of molten iron and steel over a wide range of workshop and laboratory conditions. Observations of true temperature were made with immersion thermocouples, and correlated with apparent temperatures indicated by optical pyrorneter readings taken on the pouring stream as it passed over the lip of the crucible. The emissivity of Armco iron was shown to be of the order of 0.4, rising slightly with increasing temperature. But for plain carbon steels containing up to 1.0 pct carbon the emissivity was shown to fall slightly with increasing temperatures. The results of their investigation are in agreement with those of Guthmann.9 Naeser,10 Spencer," Todd5 and Hase6 in regard to the relation between emissivity and temperature for plain carbon steels. However, Goller12 has found a rise of emissivity with increasing temperature for the same steels. Results of several investigations are given in Fig 1. Measurement of True and Apparent Temperatures The necessity for an accurate optical temperature scale for liquid iron in studies of gas-metal equilibria led to this investigation. Experimental measurements were carried out in the induction furnace used by Dastur and Chipman13 in their studies of the reaction of hydrogen with oxygen in liquid iron. The furnace as modified for this work is shown in Fig 2. The atmosphere of the furnace was a mixture of purified argon with hydrogen containing a small controlled amount of water vapor. Gases were preheated by means of a platinum-10 pct rhodium resistance coil. The stream of hydrogen sweeping across the surface of niolten iron vir-

Jan 1, 1950

By James A. McGurty, Walter J. Koshuba, Samuel G. Gordon, Gilbert E. Klein

ONE of the problems encountered in working with metals at elevated temperatures is the instability resulting from solid-solid diffusion at a -common interface. A determination of the nature and magnitude of this phenomenon is important as related to structural properties of materials potentially useful in high temperature applications. This paper is concerned with the solid state reaction between metallic molybdenum and beryllium at elevated temperatures. In the older literature,' there were no known inter-metallic compounds in the system Be-Mo, and the list of beryllium intermetallics was rather small. New compilations have been made by Smithells' and by Taylor," listing all the then known beryllium binary intermetallic compounds. In addition to these, some new phases have just been reported' in the system Zr-Be and some further compounds of the type MBe,3 have been currently described. The new compound MoBe,, which is reported upon in this paper differs considerably from the above mentioned MBe13 group, and will be discussed in detail. Diffusion Study The nature of the solid diffusion at a Mo-Be interface was determined by sealing a beryllium rod inside a molybdenum capsule and heating at a temperature of 2000°F' (1100°C) for 100 hr. The molybdenum capsule was fabricated from % in. swaged molybdenum rod obtained from the Fansteel Metallurgical Corp. The beryllium metal was obtained from Brush Beryllium Corp. as % in. cold-drawn rod. This material assayed 99.05 pct Be and contained as impurities 0.84 pct Be0 and 0.19 pct Be2C. The molybdenum capsule was % in. in OD x 2 in. long. To prepare it, a concentric hole 0.250 in. + 0.001 in. — 0.000 in. in diam was drilled and reamed in one end of a rod to a depth of 1 '/2 in. A 1 in. long beryllium rod 0.250 in. + 0.000 in. — 0.001 in. in diam was pressed into the molybdenum capsule. A molybdenum plug 0.250 in. & 0.001 in. in diam x 9/16 in. long was then used to seal the beryllium in place. The capsules were placed in a molybdenum resistance furnace and heated at 2000°F (1100°C) for 100 hr. On cooling, the specimens were cut and examined metallographically. Fig. 1 is a micrograph at X250 of a portion of the interface from a transverse section. Four phases are clearly visible, with sharp boundaries between them. Phase A is a section of the molybdenum capsule; phase B is the molybdenum-rich intermetallic composition MoBe,; phase C is the beryllium-rich compound MoBe13; phase D is a section of the beryllium rod. All phases were readily polished to a high metallic luster. The molybdenum-rich phase has a pronounced purple tinge. The beryllium-rich phase (C) is only slightly darker than the pure beryllium. In polarized reflected light, however, it shows striking birefringence between crossed Nicols. The black areas represent flaws or pores in the material. A small representative amount of powdered material from each of the phases was carefully removed under the microscope with a diamond tool. With this material, powder X-ray diffraction patterns were made for the identification of each phase. Table I lists the X-ray diffraction spacings and corresponding indexes characteristic of these intermetallic compounds. Synthesis To establish the formula of the new intermetallic compound, X-ray diffraction patterns were made from powders obtained from solidified melts of known composition. The syntheses were made by

Jan 1, 1952

By W. S. Ayres

I. INTRODUCTION. THIS cavern was discovered Oct. 22, 1904, by Mr. Charles H. Deutschman, in company with whom I made, May 29 to June 3, 1905, at the request of Mr. Howard Douglas, Superintendent of the Canadian National Parks, the first exploration of it for the Canadian government. The results were stated in a paper, orally presented, with lantern-views from my photographs, at the British Columbia Meeting of the Institute, Victoria,, B. C., July 5, 1905.* The present paper embodies also the results of a second examination, made Oct. 25 to 29, 1905. The accompanying map, Fig. 1, will serve as a guide to the following description. II. LOCATION. The cavern is situated at snow-line, at the head-waters of Cougar creek, on the west slopes of the Selkirks, about 2 miles north from Ross Peak water-tank, and 5.5 miles west from Glacier House, on the main line of the Canadian Pacific Railway. It was then reached by an arduous climb from the water-tank, up the ravine of Cougar creek, for 8,000 ft. (2,000 ft. of altitude) over rock- and snow-slides, and through a thick tangle of alders. But an easy and very picturesque trail has, during the past summer, been opened by the government from Glacier House. Figs. 2, 3 and 4 represent views, not heretofore published, of the grand scenery of this region, so rapidly becoming the-object of attraction to thousands of tourists from all parts of the world. These views, as well as those shown in. Figs. 5, 6, 7, 8

Jan 1, 1907

By R. E. Crockett

MAGNETITE mining and milling in the Eastern States was at capacity during 1940, owing to the heavy industrial, defense, and war demand, coupled temporarily with the almost total stoppage of imports of foreign ores other than those under American ownership. In New York State the active mines were those operated by the Republic Steel Corp. at Mineville and Lyon Mountain. Republic's new concentrating mill at Port Henry, handling the Mineville ores, went into production about the first of April. Other large magnetite deposits in New York are currently being prospected and studied and may be under development in the near future. In New Jersey the Mt. Hope and

Jan 1, 1941

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes' They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.' The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By A. E. Powers

YEARS of experience and research have shown that molybdenum, tungsten, and vanadium are among the most useful and effective elements in augmenting the high-temperature strength of heat-treatable, ferritic steels. Grün, for example, in conducting an early survey of the strengthening effects of various elements in annealed, low-carbon steel at 750° and 930°F (400° and 500°C), found molybdenum and vanadium to be the most effective.' Holtmann comprehensively studied the strengthening effects of molybdenum and vanadium in quenched and tempered steels at 930°F as a function of microstructure and carbon content.' He found creep strength to be related to the saturation of the austenite at the austenitizing temperature, such that strength is increased by alloying until the y loop is reached—the terminus of complete austenitization. Beyond this degree of alloying, the inability to heat treat will result in lower strength, at least for low and moderate creep temperatures. Tungsten, owing to higher cost than molybdenum, has been little used in ferritic high-temperature steels. As a result, very few investigations have been made of its high-temperature strengthening ability, and reliable data on its effectiveness are not available. Grün rated tungsten far less effective than molybdenum at 930°F (500°C) on a weight-percentage basis.' However, Tammann has found that tungsten is as effective as molybdenum in raising the recrystallization temperature of iron. For this reason Smith, in a review of the subject, has advocated a re-examination of the influence of tungsten on the high-temperature strength of steel.' In any study of the effects of alloying additions on high-temperature properties, recognition must be made of the many variables involved, some of which can be controlled but have been ignored in innumerable investigations of the past, and some of which are difficult or even impossible to control. One cannot, for example, assign a definite strengthening index to any one alloying element, for this will be dependent upon the microstructure (heat treatment and mechanical treatment), testing con- ditions (temperature, time, and stress), and the complete composition of the steel (accompanying alloying elements, impurities, etc.). One ever-appear ing variable, hardness or tensile strength at room temperature, may be eliminated by heat treating all of the alloys to a single hardness level. An attempt may be made to control the variable of primary quenched structure by oil or water quenching the test specimen. The control of such variables may not be possible in cases of widely varying compositions, but at least such deviations should be recognized. Material and Procedure The alloys, made as 30-lb ingots in an induction furnace, all had the same base composition of about 0.18 pct C, 0.85 pct Mn, and 0.48 pct Si. They were grouped as follows: Mo Group—Containing up to 5.2 pct Mo. W Group-Containing up to 6.0 pct W. V Group—Containing up to 3.3 pct V. Mo-V Group—Containing up to 2.7 pct Mo and up to 1.4 pct V. Mo-W Group—Containing up to 2.5 pct Mo and up to 2.5 pct W. The steels, listed in Table I, were forged to ¾ in. sq bars and the material for the high-temperature, rupture-test specimens was further swaged to %-in. round bars.

Jan 1, 1957

By Rollin E. Hook, Attwell M. Adair

The yield and fracture behavior of recrystallized chromiztm have been studied in order to gain an understanding of the recrystallization embrittlement-rheotropic recovery phenomenon. The duc tile-brittle tensile transition temperature of recrystallized chromium was found to vary from 225 ° to -80°C as the ratio of specimen diameter/mean planar grain size decreased. The applicability of this observation to other bcc metals is briefly discussed. Brittle fracture in recrystallized chromium was found to be initiated predominately from intercrystalline rupture nuclei. Single crystals exhibit a high degree of ductility at 23 "C. The experimental data indicate that grain boundaries play a significant part in the yield and fracture behavim. Pres training significantly reduces the transition temperature, and high temperature aging does not result in re-embrittle-ment until complete recovery or re crystallization occurs. SEVERAL theories have been used to explain the recrystallization embrittlement-rheotropic recovery phenomenon in chromium. Wain, Henderson, and ohnstone' propose a Cottrell dislocation locking mechanism due to nitrogen, and Weaver and Gross and weaver 3 propose a strain-induced precipitation mechanism involving a chromium nitride precipitate. The researches of many investigators seem to leave little doubt that brittleness in chromium is promoted by interstitial impurities. Smith and seybolt4 have shown that the ductile-brittle transition temperature is lowered as the interstitial content is reduced. weaver3 provides evidence for a 150°C reduction in the tensile transition temperature as the nitrogen content is reduced from 20 to 5 ppm. Maykuth and affee' have suggested that the amount and orientation of grain boundary impurities may be responsible for the brittle nature of recrystallized chromium. This suggestion was based on their findings that wrought iodide chromium possessing a fiberous grain structure is ductile in tension at room temperature while a recrystallized grain structure is completely brittle. Previous investigations have not studied this phenomenon sufficiently to determine its cause. Perhaps this has been largely due to previous experimental findings that brittle fracture observed in chromium has been almost entirely transgranular.' In addition McNeil and imb,' who investigated coarse-grained as-cast chromium, describe the point of initiation of fracture as cleavage, close to the (100) plane, near or at grain bound-daries, or at included particles or voids. However, Hook, Adair, and ipsitt found that fracture in coarse-grained recrystallized chromium is initiated by intergranular rupture and then propagates nearly entirely by cleavage. This result, together with their finding that room temperature ductility in bending is observed for single crystals and coarse-grained polycrystalline specimens for which the number of grains through the specimen diameter is small, suggests that grain boundaries may play an important role in the brittle behavior of chromium. The recrystallization embrittlement problem can be resolved into two questions. These are, whether the controlling mechanism is predominately one of crack initiation or crack propagation, and whether brittle fracture is initiated predominately by slip or twin induced intergranular rupture or by cleavage. The following research was designed to study the role of grain boundaries on the brittle fracture of chromium in an effort to resolve these questions. EXPERIMENTAL PROCEDURES, RESULTS, AND DISCUSSION General Procedure. All tensile specimens (except 0.04 in. diam wires) were prepared from 1/4 in. diam swaged rod fabricated from one ingot. Details of fabrication are given elewhere. The results of impurity analysis for the swaged rod and for the

Jan 1, 1963

By P. G. Meikle, C. T. Holland

The effect of the condition of friction upon the ultimate unit compressive strength as determined between the compressed faces of precisely machined coal specimens and specially prepared testing platens has been examined. Reductions of 30 to 40% in the ultimate unit compressive strength of these model coal pillars have been verified when lubricants areused between the faces as compared to non-lubricated faces. Increase in unit compressive strength due to confinement at each of three levels of friction appears to follow generally the widely accepted "1/2 power law", i.e. S - C (L/T)1/2 where S is the unit ultimate strength, C is a constant dependent on the coal being tested and the coefficient of friction acting at the compression surfaces and L and T are the least width and thickness of the specimen, respectively. Results suggest that the surface condition of both the specimen and platens should be mentioned in detail in conjunction with compression testing, for although the term (L/T)1/2 is adequate for all practical purposes, the coefficient C is directly dependent on the condition of interfacial friction, all else remaining constant. One phase of the investigation of the confining effect of friction on the ultimate unit compressive strength of small coal specimens has recently been completed at the School of Mines of West Virginia University. The efficient control of ground is of fundamental importance to successful mining operations and the design of support pillars has always presented the mining engineer with a difficult and intriguing engineering problem. Since about the turn of the century, many investigators have performed extensive laboratory tests on small coal specimens in efforts to solve some of the perplexing problems of strata control and pillar action in coal mines. A detailed review of this work would serve no purpose here, but a brief mention of the more significant contributions is in order. Muller16 was perhaps the first to illustrate the effect of confining pressure on the strength of coal specimens in compression. His work has recently been more carefully expanded by the experiments of Murrell17 in Great Britain. Rice and Enzian l9 observed that as the size of cubical test specimens increased, the unit compressive strength decreased. These observations were later supplemented by Lawall and Holland, 13 by Greenwald4,5 et a1 at the U. S. Bureau of Mines, by Gaddy3 as well as by Steart,22 Millard15 et a1 and Evans2 et al. Gaddy3 seems to have been first to quantify this relationship with his equation: S = K/vd , where S - ultimate unit compressive strength (psi), K = a constant dependent on the coal, and D =edge dimension (in inches). Holland7 concluded that the strength of coal as affected by lateral dimensions and thickness could be expressed as where K = a coefficient dependent upon the coal, L = least width of pillar (in.) and T = thickness of pillar (in.). Data supplied by this formula have been compared to the estimated stresses in pillars that had been standing for long periods in coal mines and in the cases so far studied the results indicate that the formula predictions are sufficiently accurate for engineering purposes (Holland11 ). This equation therefore is believed to be the simplest and most accurate tool available at the present time for approximating the strength of a coal pillar (over a specified range of L/T) in situ. However, Holland7,9 has indicated that friction between the coal pillars and the top and bottom rock

Jan 1, 1965

By Paul A. Flinn, Jean-Marie Robert Genin

The MCssbauer effect was used to study the distribution of carbon in Fe-C alloys of high carbon content during room-temperature aging. In freshly formed rnartensite the carbon distribution is approximately random; carbon clustering occurs dun'ng aging. In the retained austete the carbon atoms are isolated, suggesting an efiective repulsion; and no rearrangement during room-temperature aging is evident. The kinetics of the carbon clustering in martensite has been studied in detail at 0" . 10". and 20°C. The time and temperature dependence observed is sinzilar to that reported for a variety of other aging effects, such as resistance change, hardness increase, and recovery of internal friction. The stabilization of the martensite kransformation also appears to be related to the clustering effect. DESPITE extensive efforts since the early days of Reaumur, the mechanism which provides the strengthening of steel remains controversial in many cases for several reasons: 1) The structure of as-quenched martensite is not well-determined. 2) Experimental methods capable of distinguishing between various hardening mechanisms are not well-developed. 3) The temperature of formation of many low-alloy martensites is so high that the martensite formed during quenching may be already tempered to some extent before any observation. Among all the hardening phenomena, the most puzzling one occurs at room temperature, where no structural changes have been detected by the usual methods of X-ray diffraction or electron microscopy. However, a new and more sensitive technique became available with the discovery of the MBssbauer effect. This effect makes possible the detection of changes in the local environment of iron atoms in solid solution. It has been extensively used in the study of substitutional alloy systems, for example, Fe-Al,1 Fe-Si,2,3 Fe-Rh,4 and Fe-Ni.5 Making use of the possibility of obtaining new structural information, we undertook an investigation of the aging of high-carbon Fe-C martensite to follow the structural changes involved in the aging at room temperature. Preliminary results6 showed that a clustering of the carbon atoms occurs with time. A systematic study of the kinetics of the process showed a striking similarity to the kinetics of stabilization of the marten-sitic transformation, thus suggesting further investigation of the relationship. EXPERIMENTAL TECHNIQUE To eliminate difficulties with the aging of martensite prior to the first experimental measurements, we needed an alloy with an M, temperature not above room temperature. Other investigators7 were misled by results obtained on alloys which transformed above room temperature and underwent structural changes prior to the first Mossbauer measurements. Winchell and cohen8 dealt with this difficulty by using a third element, nickel, to depress the MS below room temperature. The presence of nickel did not seriously interfere with hardness or resistivity measurements, but it would complicate the interpretation of the Mossbauer data by increasing the variety of iron environments. We chose, therefore, to obtain the necessary lowering of the M, simply by increasing the carbon content. After the first quench to room temperature, our specimens are retained austenite, which we later quench into liquid nitrogen. The martensitic transformation takes place suddenly, so that the as-quenched condition of the samples is retained, since the temperature is low enough to prevent any carbon diffusion. A Massbauer spectrum at 77°K can be taken and analyzed; after an appropriate up-quenching to the aging temperature, a new Mossbauer measurement at 77°K can be made. Fig. 1 shows a typical cycle of experiments. The samples were foils 25 p thick of high-purity

Jan 1, 1969

By H. I. Aaronson, C. Laird

Cold rolling by 50 pct a A1-4 pct Cu alloy containing many 0' plates has been found to accelerate markedly the transformation of 8' to 0 upon further aging. Although the basic mechanism of this transformation remains unchanged by plastic deformation, the nuclea-tion kinetics of 8 become appreciably more rapid and also less dependent upon temperature. Particularly at lower aging temperatures, rounded idiomorphs replace several faceted rnorphologfes. The rates of growth of 9 idiomorphs in deformed specimens aged at 300°C are appreciably more rapid than simple volume diffusion control allows. This observation is shown to be explained by an excess vacancy, rather than by a dislocation Piping mechanism of growth. ThE rather complex phenomenology of the 8' —8 transformation in Al-Cu alloys has been recently elucidated in considerable detail by means of transmission electron microscopy.'-4 This technique was also employed in the present investigation in order to examine the effects of plastic deformation upon the transformation of 8' to 8. The mechanism of the transformation in undeformed Al-Cu alloys has been established as the following sequence of events.1"4 The first step is the nucleation of 9 at (Y:8' boundaries. Nucleation of a 0 crystal takes place, however, at only a very small proportion of the 8' plates present. Each 0 crystal simultaneously consumes the host 8' plate and the a! in the immediate vicinity, with growth into a being the rate-controlling process. The remaining 8' plates are then dissolved as they fall under the concentration shadow of the growing 8 crystals. The evidence on the effects of plastic deformation upon these processes is intriguing, but much less detailed. The careful X-ray studies of Graf and Guinier have shown that the aging times required to form detectable amounts of 8' and 8 are reduced by prior cold working. Thomas and Nutting confirmed these results by replication electron microscopy. Nile-shwar,* on the other hand, reported that creep deformation decreases the rate of formation of 0. While this difference may have been caused by the use of concurrent rather than successive deformation and ag- ing, the X-ray technique which he used was able to monitor only the 0 phase. It is thus possible that the times needed to form 8' were increased moreg than the kinetics of 8' — 8 transformation were accelerated. At 90 pct deformation by cold rolling, Graf and Guinier found that the usual 0' —0 8 sequence is reversed: 0 forms first. von Heimendahl 10 confirmed this result with transmission electron microscopy. Pollard and Nutting, 11 and more recently Driver and Barrand, 9 having used the same technique, report that 9 also forms first during creep deformation. In the present study, the maximum amount of deformation was limited to 50 pct reduction by cold rolling in order to insure that 8 formed principally by the decomposition of . I) EXPERIMENTAL PROCEDURES This investigation was conducted on an Al- 3.93 pct Cu alloy, prepared as previously described. 4 Morphological and crystallographic effects of plastic deformation were studied in specimens annealed 6 hr at 548°C, quenched, and then aged for either 3 or 8 hr at 250°C to form large numbers of 0' plates. After cold rolling to a 50 pct reduction in thickness, the

Jan 1, 1969

By E. S. Lenker, H. J. Van Hook

A complete swies of solid solutions has been found between the compounds InAs and GaAs Below the solidus. The melting relations determined by differential thermal and static quenching technzques, indicate that the liquidus and solidus are of the simple ascendant type. No evidence of unmixing of the homogeneous solid solutions was observed at sub-solidus temperatures. A quenching method for locnting the solidus, using X-ray diffraction techniques, is described in some detail. THE semi-conducting properties of compounds formed by various combinations of the less familiar intermetallic elements have created an increasing interest in the phase relations in systems involving these elements. The complete phase diagram of such a system, containing a compound of special interest, will often provide information as to the most favorable conditions for preparing large crystals from a melt, as well as specifying the temperature stability of the crystalline phase or phases produced. In view of the current importance of gallium arsenide in semiconductor research and of the structural similarities of indium arsenide, it was thought that the complete phase relations of the system InAs-GaAs should be investigated. Previous work on the system Ga-As by Koster and homa' and on In-As by Liu and peretti2 has shown that GaAs and InAs are the only compounds formed, having melting points of 1238° and 942°C, respectively. In a survey of various systems of elements from groups IIIb and Vb, spengler3 also re- Mines Ltd., for his continuing encouragement and for permission to publish the results of this work. ports complete miscibility of gallium, indium, and arsenic in the liquid state. In a partial investigation of the InAs-GaAs system, Woolley and smith4 found extensive solid solution throughout the alloy range. Their subsolidus work, however, was inconclusive at temperatures below 900" and they did not determine the liquidus relationships of the system. PRESENT INVESTIGATION The starting materials used were high-purity gallium, indium, and arsenic. The method of preparation of the compounds follows that devised by M. Shafer and is described in detail in a paper by Shafer and eiser.' The end-member compounds, GaAs and InAs, were first prepared by reaction of the elements in the desired proportions in evacuated silica glass vials. The vials were rotated in a furnace as the temperature was slowly raised to insure rapid and complete reaction at low temperatures. Thereafter the starting materials, GaAs and InAs, were melted by heating the sealed vials to 1300" and 1000°C, respectively; the vials in this case were filled as completely as possible to keep the vapor space small and thereby minimize the loss of arsenic to the vapor phase. Ten binary mixtures of these compounds were then prepared by reaction of the powdered material in the solid state just below solidus temperatures. At 900C preparations containing 3, 5, 8, 10, 25, 35, 50, and 75 mol pct GaAs were found to be single homogeneous phases, indicating a complete series of solid solutions between GaAs and InAs. Moreover, it was discovered that the homogeneity of any crystalline binary preparation could be very accurately checked by X-ray diffraction because of the large differences in unit cell dimensions of the end membe5s. The cubic lattice constant ofor GaAs is a = 5.652A and that of InAs is a = 6.061A

Jan 1, 1963

By R. W. Harper, M. C. Fuerstenau, J. D. Miller

Data were obtained with hematite with octyl hydroxamate and oleate as collectors to determine the mechanism of collector adsorption and also to establish the roles that conditioning time and temperature assume in this system. The presence of hydroxy complexes of iron are apparently necessary for chemisorption of collector to occur, and it appears as if extended conditioning times and elevated temperature promote greater dissolution of the mineral and hence greater concentrations of hydroxy complexes. Data were also collected with two natural hematitic ores. With one ore that was ground to 70% - 15u, an addition of 0.4 lb per ton hydrox-amate resulted in a final concentrate recovery of 86% at a grade of 64% iron. Satisfactory concentrate grade could not be obtained with fatty acid under these conditions. The effect of conditioning time prior to the addition of collector was also examined with another ore. When the ore was conditioned for 3 min, 19% of the iron was recovered in the concentrate at a grade of 67% Fe. With a conditioning time of 7 min, 73% of the iron reported to the concentrate at a grade of 62% Fe. These products were obtained with an addition of 0.2 lb per ton hydroxamate. This ore also responded well to flotation with fatty acid. The use of potassium octyl hydroxamate as a collector for iron oxide has been the subject of an earlier study.1 From this initial study, it was suspected that hydrolysis of surface ferric iron was involved in collector adsorption. More recent work in other systems has shown that slight mineral dissolution, followed by hydrolysis of cations common to the mineral lattice, is apparently necessary, and that adsorption of these hydroxy com- plexes probably occurs prior to the adsorption of collector. In view of these facts, work has been continued on the hydroxamate-hematite and oleate-hematite systems to gain better insight into the mechanisms of collector adsorption on iron oxide. Microflotation experiments in conjunction with infrared analysis were used in this regard. In addition it was felt necessary to establish more clearly the responses that can be obtained from natural ores when hydroxamate is used as collector as compared to those obtained when fatty acid is used. Experimental Materials and Techniques Pure potassium oleate, potassium octyl hydroxamate, synthesized from hydroxylamine hydrochloride and methyl octanoate, and a distilled Tall Oil were employed as collectors. Conductivity water was used in the

Jan 1, 1971

By Frederick F. Frick

SPONGE iron as produced at Anaconda is a fine, -35 mesh, impure product, about 50 pct metallic iron, obtained from the reduction of iron calcine at a temperature of 1850°F by use of coke resulting from slack coal. The metallic iron particles are bulky and spongey and precipitate copper readily and rapidly from a copper sulphate solution. Investigation of the treatment of Greater Butte Project, Kelley, ore at Anaconda early showed the desirability of using sponge iron as a precipitant for the copper in solution resulting from desliming of the ore in a dilute sulphuric acid solution. Anaconda had done considerable work on the production of sponge iron in 1914 for use as a precipitant of copper from leach solutions. Some success and considerable experilence were attained at the time. indicating that, sponge iron might be successfully made by a modification of the process used in 1914, a batch process in which an iron calcine was reduced by means of soft coke, resulting from noncoking coal, in a Bruckner-type revolving horizontal cylindrical furnace widely used 50 years ago. The coke and calcide formed the bed in the Bruckner furnace, which was rotated at about 1 rpm. The bed was brought to a temperature of about 1800°F by means of an oil flame over the surface. Although results were reasonably satisfactory, they did not warrant full development of the process at that time. A good deal of work has been done in the last 50 years on the production of sponge iron. The objective in some cases has been the production of a precipitant for copper from solution, but the bulk of the work has been done for the production of open-hearth steel furnace stock. The production of an open-hearth stock presents two problems rather than one: first, producticon of the sponge iron, and second, what is perhaps of equal difficulty and importance, conversion of the sponge iron into a form suitable for use in the open-hearth furnace. So far as is known to the writer, none of the sponge iron processes tried in the past have proved to be economically feasible. However, Anaconda had a combination of conditions appearing to justify an attempt to produce sponge iron which would serve for the leach-precipitation-float process. It was thought that the process used in 1914, if changed to a continuous one, might work out satisfactorily. The following favorable conditions at Anaconda justified the investigation: 1—A sufficient tonnage of good grade iron calcine resulting from the roasting of a pyrite concentrate in one of the acid plants, at substantially no cost. 2—Reasonably cheap natural gas. 3-—The fact that there was no need for production of a high grade product. 4— The fact that there was no need for obtaining a consistently high reduction of' the iron in calcine. A small revolving Bruckner-type furnace about 2 ft ID by 4 ft long was set up for early pilot work at the research building. This pilot furnace showed that a satisfactory product could be obtained at reasonable cost. It also indicated a marked advantage in preceding the reduction furnace with a furnace of similar size and capacity for preheating and roasting out any residual sulphur from the feed. The small furnace was operated for several months, various details of the process were worked out. and sponge iron was produced to supply a pilot LPF plant which treated 300 lb of Kelley ore pel- hr. Later a second pilot furnace 5 ft in diam and 12 ft long inside was set up at our reverberatory furnace building. This furnace confirmed the data of the small furnace and gave a basis for design of the final plant. At Anaconda a pyrite concentrate, running about 48 pct S, is recovered from copper concentrator tailings by flotation. This concentrate is roasted to sulphur of 3 pct or less at the Chamber acid plant. The iron calcine contains about 57 pct Fe and 18 pct insoluble. The iron calcine feed, as mentioned before, is re-roasted and preheated in a reroast furnace preceding the reduction furnace. Both are of the Bruckner type. The reroasted calcine is fed into the reduction furnace at 800" to 1000°F along with 30 pct slack coal. In the feed end of the furnace the volatile is burned from the slack, giving a soft coke which readily serves for reduction of the iron. Hard metallurgical coke will not serve the purpose. since it does not reduce CO readily at a temperature of 1850°F. All indications are that the actual reduction of the iron is accomplished by carbon monoxide below the surface of the bed, which is 30 in. deep at its center. Apparently there is a constant interchange: Fe²O³ + 3CO = 2Fe - 3CO², CO² + C = 2CO Actually iron oxide is reduced by CO at somewhat lower temperature than the 1850 °F used in the process. but this temperature is necessary to obtain a satisfactory rate of furnace production. The furnace atmosphere is generally reducing, and typical blue carbon monoxide flames satisfactorily cover the bed. Gas flames from four 3-in. Denver Fire Clay Inspirator burners are played directly on the bed, which is slowly cascaded by the 1 rpm of the furnace. An excess of coke is necessary to assure maintenance of good reducing conditions in the furnace bed. Part of this coke is recovered for re-use.

Jan 1, 1954

By J. R. Low, M. Gensamer

During the course of an investigation into the drawability of automobile-body sheet steel, it became apparent that certain advantages would be possessed by a deep-drawing steel with a very low yield strength, but almost normal tensile strength, provided a reduction in yield strength could be accomplished without sacrifice of ductility and fine grain size. It would also be desirable to have this steel free from strainaging; that is, free from the tendency for the yield point to return after it had been eliminated by straining. It was known that wet hydrogen treatment acted to eliminate aging, but as carried out by other investigators, at relatively high temperatures, this treatment resulted in grain coarsening. It has been established by some of the experiments reported in this paper that all of these objectives can be accomplished by treatment in wet hydrogen at a low temperature, in the neighborhood of 720°C. The time of treatment is relatively short (about 3 hr. to completion with 20-gauge sheet) if the water content of the hydrogen atmosphere is made fairly high, say almost 30 per cent by volume. At this temperature, the grain size remains fine in the time required. After this treatment sheet reduced the usual amount by cold-rolling has a grain size of about A.S.T.M. No. 7. The yield point is completely eliminated, and the yield strength is reduced to a very low value, in the neighborhood of 15,000 lb. per sq. in. The stress-strain curve departs gradually from the straight-line elastic part after the fashion of nonferrous deep-drawing alloys. This elimination of the yield point is accompanied by a very low indentation hardness; for example, 32 Rockwell B or even lower. There is no aging as measured by increase in the yield strength upon aging at room temperature or for 3 hr. at 200°C., after stretching about 10 per cent in tension. Tensile strength is only slightly less than the box-annealed sheet, seldom dropping much below 40,000 lb. per sq. in. Elongation is practically unchanged, or increased slightly. The term yield point, as here used, refers to the phenomenon of heterogeneous deformation occurring at a substantially constant load, observed principally in annealed low-carbon steels. If such a steel is loaded in tension, the load increases steadily with elastic strain, suddenly falls, fluctuates slightly about some constant value for a time and then begins to rise again as deformation proceeds. The maximum initial load before the sudden drop is generally called the "upper yield point"; the value of the load where deformation proceeds at a

Jan 1, 1943

By J. T. Michalak, H. W. Paxton

The recovery of the initial flow stress of poly-crystalline iron is characterized by a) a logarithmic time dependence; b) an increasing activation energy with increasing recovery; c) an increased ?,ate and fraction of recovery with decreased temperature of deformation; and d) an increased rate with increased deformation. Isochro)ml studies of the recovery of single crystals revealed more sluggish recovery. The original flou3 stress of single crystals could be regained by recovery anneals at 800"or 900°C. ThE great majority of the theoretical treatments and experimental studies of strain-hardening have been concerned with the close-packed lattices.' Very little effort has been expended on the bcc structure so that the theory of work-hardening of this lattice is essentially nonexistent. The limited amount of experimental data resulting from the direct studies on silicon-iron,2 low-carbon steel,3 and purified irons4"7 does not as yet permit a detailed analysis of the strain-hardening. Studies concerned with the effects of annealing following deformation have been few in number," have been somewhat limited in extent, and have had the disadvantage of using irons containing a substantial impurity content. The present research was undertaken to augment the limited knowledge we have of the characteristics of a bcc metal as regards strain-hardening and recovery from the strain-hardened state. The recovery of the flow stress has been employed since it was felt that the stress associated with the hardened state gives at least a fair qualitative description of the state of the imperfections causing the hardening. The study was concerned primarily with the recovery of flow stress following strain-hardening of polycrys-talline, zone-melted iron as a function of the amount of deformation, the temperature of deformation, and the time and temperature of the recovery anneal. A limited investigation of the recovery of the initial flow stress of single crystals of this same material as a function of the recovery temperature was also conducted in conjunction with the Lambot X-ray technique." MATERIAL The zone-melted iron used in this investigation was obtained through the courtesy of the American Iron and Steel Institute and Battelle Memorial Institute. The analysis, as given by the supplier indicated a maximum impurity content of 0.02 wt pct excluding those impurities listed in Table I. (The actual impurity content is very probably less than this since detection limits were considered as the amount of a particular impurity level.) Also listed in Table I are the interstitial impurity contents of the iron at various stages of experimental work indicating that these im-

Jan 1, 1962

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

By Alexander Squire

A brief study of the effects of material and processing variations upon the tensile properties of steel formed from mixtures of iron and carbon was made in order to provide information regarding the properties obtainable in iron-carbon compacts as influenced by forming pressure, sintering temperature, and graphite particle size. Sintered steels formed from mixtures of iron and graphite have been studied by Stern,' who investigated the effect of various percentages of graphite on compacts formed from electrolytic iron that were repressed and heat-treated after sintering. A further study, by Stern and Greenberg,l is concerned with the heat-treatment of steels formed by the car-burization of iron compacts, and Margolies3 has reported work on the simultaneous sintering and carburization of iron-powder parts. Glauch4 investigated the effect of various types of graphite on the properties of iron-carbon powder alloys but did not determine the effect of different particle sizes of the same graphite alloyed with different types of powder. In the investigation reported in this paper, powders typical of those produced by electrolytic deposition and the decar-burization of shotted steel scrap were used. The powders were mixed by tumbling in a jar mill with graphite powder ground to an average particle diameter of 2, 4, 6, and 16 microns (as determined by microscopic measurement). The properties of the iron and graphite powders are presented in tabular form as Table I. In order to obtain the maximum information from a minimum number of test specimens, the study was divided into two sections with one set of specimens treated identically in each section as a basis for comparison. In the first section, iron powder produced by the shotting and subsequent decarburization of scrap steel was mixed with 2-micron graphite powder, pressed at 50,000, 100,-000, and 200,000 psi, and sintered in hydrogen at 1200°C for the periods of time ranging from 15 to 120 minutes. In the second section of the investigation, electrolytic iron powder was mixed with graphite of an average particle diameter of 2, 4, 6, and 16 microns, pressed at 100,000 psi, and sintered at temperatures ranging from 1000° to r200°C'. for periods of time of 30 to 180 minutes. By following this procedure an indication of the effect of the following variables upon the density and tensile properties of iron-carbon powder compacts was obtained: (I) forming pressure, (2) sintering time, (3) particle size of graphite powder, (4) sintering temperature, (4) type of iron powder.

Jan 1, 1947

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