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By R. F. Lynch, J. D. Wood

The Al-1.0 pct Mg alloy 565 7 was studied using optical microscopy and electron microprobe X-ray analysis. Constituent particles were found to exist inter-dendritically in the as-cast material in a region of precipitate free a -aluminum. Five phases besides a fine precipitate and a-Al were identified in the cast structure: Fel3, Fe2Al7, Mg2Al3, CUMgAl2, and Cu2FeAl7. Thermal treatments conducted for 100 hr at 1180°, 1130°, 1080°, 1030°, 980°, and 880° F revealed a general dissolution and spheroidization of the in-terdendritic constituent network observed in the cast structure. The principal constituents present in the thermally treated structures were FeAl3 and Fe2Al7 with the relative amount of Fe2A17 to FeAl3 increasing with a decrease in the treatment temperature. The phases Present in the wrought structure were identical to those observed after the thermal treatments, with the constituent particles strung out in the direction of rolling. ALLOY 5657 is a nonheat-treatable commercial purity Al-1.0 pct Mg alloy utilized extensively because of its bright finishing characteristics. This investigation was conducted to determine the constituents present in 5657 alloy, and to study the effect of extended thermal treatments on morphology. Numerous studies have been carried out to establish the equilibrium diagrams for various aluminum systems,1-3 with phase identification based on X-ray analysis, morphology, and the etching response of relatively large particles. Phragmen4 conducted a study of the phases in aluminum eutectic systems and compiled a "corrected" table of etching responses, drawing on his work plus that of Schrader,5 Keller and Wilcox,6 and Mondolfo.7 A review of the original work of Keller and Wilcox, and Mondolfo, which was concerned with the constituents found in commercial alloys, reveals that in numerous cases their etching responses differ from those reported by Phragmen and from each other. These inconsistencies may occur because a specific constituent will react to a given etch in a varying manner depending upon its size, the elements dissolved in the phase, the other constituents surrounding a phase, and the solute content of the matrix. Work with a commercial orientation was conducted on alloys 2024 and 3003 by Sperry8,9 and on alloy 3003 by Barker,10 where the relationship between the phase diagram and the nonequilibrium structure of an alloy was examined. Backerud11 investigated the A1-Fe binary system and found that at high cooling rates the equilibrium eutectic reaction forming a-A1 and FeA13 is replaced by another lower temperature eutectic reaction forming a-A1 and metastable FeAl6, a constituent first identified by Hollingsworth et al.12 Most of the above mentioned studies were conducted on materials having a significantly greater alloy content than 5657 alloy, where the relatively small size and sparse distribution of second phase particles hinders the process of identifying constituents. EXPERIMENTAL PROCEDURE Material with a composition as given in Table I was examined in the as-direct chill cast, hot rolled and cold rolled conditions, and after thermal treatment of the cast structure. Thermal treatments were terminated by a water quench. Microscopic examination was conducted under various lighting conditions following the application of standard etchants as specified in Table 11. A semi-quantitative electron microprobe X-ray analysis was conducted for Al, Mg, Fe, Cu, Si, Zn, and Ti. RESULTS AND DISCUSSION Microstructure of the As-Cast Material. Particles of second phase material were found to exist inter-dendritically, principally in regions of precipitate free a-Al, as illustrated in Fig. 1. Adjacent to the ingot edge was a region of inverse segregation, resulting in an increased amount of second phase material containing large sized particles which aided in phase identification. Phase Identification. Cast Structure. Five phases besides a-Al and a fine precipitate were identified using optical microscopy and electron microprobe X-ray analysis, as presented in Tables II and III, respectively. FeA13 and Fe2A17 are often found with Fe2A17 forming a sheath around the core of FeAl3, resulting from an incomplete peritectoid reaction. These phases have a nearly identical appearance under white light, although they are easily differentiated under crossed polarizers, as characteristically illustrated in Figs. 2(a) and 2(b), respectively. Microprobe analysis con-

Jan 1, 1970

By H. W. Knott, M. H. Mueller

The crystal structures of Ti2Cu, Ti2Ni, Ti4Ni2O, and Ti4Cu20 have been determined using powder specimens examined by X-ray and neutron diffraction. Lattice constants have been determined for all four phases using X-ray powder diffraction films. Atom positional parameters of all four phases have been determined from observed neutron intensities. X-ray diffraction calculated intensity data have been presented also for the phase Ti2Cu to point out the particular suitability of neutron diffraction in this case. Interatomic distances have been determined using the positional parameters obtained from neutron diffraction. ALTHOUGH some investigations of the crystal structures have been made of these four compounds previously,'-13 it was the purpose of the present investigation to expand the previous work in order to locate the various atoms, determine their coordinates, and to confirm or to correct some of the previous work. It was convenient to group these four compounds together since they are related chemicallv and/or structurally. The compound Ti2Cu is tetragonil; and Ti2Ni, Ti4Ni2O, and Ti4CU2O are all large fees of the same space group. Ti2Cu has been previously reported as a fee phase by Laves and Wallbaum;1 and Rostoker2 which was possibly the oxide phase, Ti4Cu20. Joukainen, Grant, and Floe;3 and Trzebiatowski, Berak, and Ramotow-ski4 have also reported a phase of this composition. karlsson5 has reported a small fct phase of the composition Ti3Cu which may be the presently discussed Ti2Cu phase. More recently Ence and Margolin6 have reported a small fct phase for Ti2Cu and the present authors7 together with Nevitt8 have briefly reported it to be a bet related to the fct with a co three times the length of the co of the fct and have also reported that this phase has a very limited composition. Further refinements will be reported which have varied some of the parameters of this bct structure slightly. Ti2Ni has been reported as a fee phase by Laves and wallbaum;1 Duwez and taylor;9 Rostoker;2 Poole and Hume-Rothery;10 and Yurko, Barton, and parr.11 In a later paper Yurko, Barton, and parr12 have given the complete structure of this phase based on an X-ray diffraction study which was independently confirmed with neutron diffraction by Mueller and knott.7 Additional crystal structure information will be given. Ti4Ti2O, Ti4Cu2O, and a number of other compounds including Ti4Fe2O have been reported as fcc phases by Rostoker,2 and more recently Nevitt13 has confirmed the Ti4Ti2O phase. Rostoker,2 however has reported diffraction lines for Ti4Fe2O which do not have all odd or all even indices. These lines, therefore, cannot be observed if this compound has a fee structure. This same error has crept into the diffraction results reported for TiNi2O and Ti4Cu20 in the ASTM powder data which has been credited from Rostoker's data. Complete crystal structures of these two phases will be presented. Although all four of these structures have large unit cells and hence do not lend themselves for completely resolved neutron powder patterns, a sufficient number of individual reflections was observed for solving the structure. They also serve as good examples of some of the advantages to be gained by using both neutron and X-ray diffraction techniques. EXPERIMENTAL PROCEDURE All of the alloys were prepared by arc melting. The starting metals had the following purity: Cu 99.999 pct, Ni 99.83 pct, and Ti 99.92 pct. Oxygen was introduced into the two oxide phases as chemically pure TiO2, with the remainder of the titanium coming from the above mentioned metal. All of the sample buttons were annealed in evacuated Vycor tubes, the two binary phases for 5 days at 700°C and the two oxide phases for 3 days at 900°C. Oxygen analyses were performed on all four phases by two independent laboratories with the following amounts of oxygen present in atomic percent; Ti2Cu-0.06, Ti2Ni-1.03, Ti4Ni2O-13.95, and Ti4Cu20-13.87. The stoichiometric amount for the oxide phases is 14.29 at. pct. Since all of the samples were very brittle they were easily reduced to a powder for diffraction measurements. The lattice constants given in Table I were determined for the four compounds from X-ray diffraction patterns of powder samples exposed to filtered copper radiation using a 114.59 mm diam Debye-Scherrer type camera using the Straumanis loading. None of the patterns showed a detectable amount of a second phase. The lattice constants were obtained from an IBM 704 computer program employing a least squares treatment with systematic correction terms as previously reported.14

Jan 1, 1963

By Shun-ichi Satoh

A NEW method of treating steel by ammonia has recently been intro¬duced into the metallurgical industry, by means of which piston cylinders of internal combustion engines, shafts and other similar steel products can be made more resistant to wear than formerly. In 1929 the writer' published the historical notes and some experiments upon nitrification. He believes that the corrosion of nitrified steel is a matter of importance and worth studying; and as there have been few studies thereof, he has conducted experiments in this respect. L. Guillet,2 in 1927, reported corrosion tests made on nitrified and cemented steels with acid and salt solutions. In 1928, 0. Hengstenberg3 reported the high resistance of nitrified steel to water vapor and air. V. 0. Homerberg4 stated that nitrified steel has high resistance to water, air and salt solution; and G. Hagg5 studied nitrified layers of iron by means of the X-ray. Though F. Hanaman6 in 1913, measured the single potential difference of steel treated with ammonia at above 650° C., no one, it seems, has ever measured the single potential difference of the so-called nitrified steels having extraordinary hardness. The writer measured the single potential differences of nitrified special steels in various solutions with the object of studying the corrosion problem and, if possible, of knowing whether any new physical property would be caused by nitrification.

Jan 1, 1932

PROF RICHARD ÅKERMAN Stockholm, Sweden ANDREW CARNEGIR New York, N.Y. DR. JAMES DOUGLAS New York, N.Y. R.A. HADFIELD Sheffield England PROF HANS HOEFER Leoben, Austria PROF HATON DE LA GOUPILLIERE Paris, France M FLORIS OSMOND Paris, France PROF DIMITRY CONSTANTIN TSCHERNOFF St Petersburg, Russia PROF DR HERMANN WEDDING Berlin, Germany

Jan 1, 1910

By Samuel B. Christy

At the last meeting of the Institute, several contributions were made to the subject of miners' aid funds. Such matters will always form important factors in the administration of large industrial enterprises. From the frequently remote and isolated position of mining properties, it is a subject that often forces itself upon the attention of the mining engineer. Local conditions are usually so variable that no single method can be found equally well adapted to all localities. At the same time, a study of different types is often suggestive and valuable, and it is with this in view that these notes are presented. The Miners' Fund of New Almaden is a remarkably successful example of what may be done for miners by a wise and at the same time firm management, by simply directing their own efforts and without incurring any great expense to the stockholders,—a practical consideration not without importance in most cases. The quicksilver mines of New Almaden are situated at a distance

Jan 1, 1885

By Magnus Troilius

For some time I have been using with great advantage, for the purpose of determining rapidly and accurately the chemical composition of gases from Siemens producers, an apparatus arranged generally like that proposed by Prof. Eggertz; * and I now take pleasure in laying before the members of the Institute a description of the apparatus and its use, hoping that some of them may find it. of practical advantage. At the end of the paper are given some results obtained and heat calculations, with the necessary data for the same. COLLECTION OF GASES. Fig. 1. Shows the arrangement for taking a sample of gas. The funnel F, which may be made of tin plate, is made to fit the test-hole. The gas passes up through the funnel and through the rubber-tubing with the glass tube K, filled with asbestos for retaining dust,, and is drawn into the upper flask by means of water flowing from the same into the lower flask. The upper flask must be completely filled with water from the beginning, so that no air remains. When filled with gas the screw-compressors are securely fastened on, and the flask disconnected from the funnel and receiver. Quart flasks, with openings at the bottom, are very suitable, and easily obtainable. COMPOSITION OF THE GASES. The ingredients found in producer gases are: carbonic acid (CO2), oxygen (0)) ethylene (C2H4), carbonic oxide (CO), hydrogen (H), and marsh gas (CH4). The nitrogen is taken by difference. CO2,O,C2H4, and CO are determined by absorption in various liquids and by observing the resulting diminution of volume. H and CH4 are determined by combustion with oxygen. Carbonic acid.—For this gas is used a solution of 16 grams of potassium hydrate in 100 C.C. of water. 4 or 5 C.C. of this solution absorb 100 C.C. of CO2.

Jan 1, 1883

By B. D. Cullity

GOLD and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,1 this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low- temperature beta form will be considered in this paper. EXPERIMENTAL PROCEDURE The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be pre- pared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsymmetrically in the camera in order to afford a basis for am-shrinkage corrections. A sample homogenized at 5o0°C gave the same diffraction pattern as a sample taken from the as-melted ingot. GENERAL RESULTS The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 ± 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the dsraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an "average" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing some- what more and somewhat less than 50 at. pct gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By B. Chalmers, Stefan Wojciechowski

Rotary oscillation of the mold has been used to produce mechanical stirring of the melt during unidirectional solidification. Al-Cu alloys (1 to 4 wt pct Cu) were solidified to study the influence of alloy composition, temperature at which intensive cooling was initiated, and intensity of stirring on the temperature distribution in the sample, the resulting structure, and the copper microsegregation at the columnar to equiaxed transition. The Proposed explanation for the equiaxed solidification in stirred castings consists of the melting off of dendrite fragments, their partial remelting in hotter liquid, and the subsequent growth of the surviving part when the temperature of the melt is lowered. This may result in the formation of a crystal network, which can stop the growth of the columnar crystals and produce the equiaxed zone. It has long been known and many times affirmed that ultrasonic vibrations or relative motion of liquid and solid can significantly reduce the length of the columnar zone and refine the grains in the equiaxed zone in ingots and castings. Because of the technological importance of these phenomena many investigations have been conducted in which ultrasonic energy or mechanical vibration,1-6 electromagnetic stirring,7"10'17 magnetic stirring,"'12 or mechanical stirring13'14 were used to produce the relative liquid-solid motion. More recently, the question of the importance of natural (or thermal) convection has been raised.15-l7 Several possible mechanisms have been suggested.l,8,18-20 They can be divided into two main groups. The first group includes such nucleation hypotheses as nucleation frequency enhancement due to cavitation at the mold wall or other surfaces; cavita-tion in the body of the liquid resulting from the pressure wave, or an agglomeration mechanism, which involves the formation of nuclei by the accretion of subcritical nuclei. The second group considers the grain-refining action to be due to crystal multiplication phenomena such as the removal of the dendrite fragments by viscous forces or by a high-pressure cycle following cavitation or by a melting-off process. Sbme recent investigations give good experimental support to the melting-off proposa1.21-23 The purpose of the present study was to examine the effect of mechanical stirring during the unidirectional solidification on the structure of alloy samples and on the solidification variables. The motion of the liquid was produced by rotary oscillation of the mold around its vertical axis.

Jan 1, 1969

By Y. Shimomura, M. Serizawa, Y. Takahashi, K. Miyagawa

The "semi-pellet" sintering method developed and currently being used at the Fuji Iron & Steel's Hirohata Works is discusssd. It is shown that the method makes fine-sized material easily sinterable and increases sinter production. The operation can be incorporated readily into conventional sintering plants. Sintering plant raw materials currently being used in the Hirohata Works consist of 40 pct pyrite cinder, 40 pct fines resulting from crushing and screening of imported ores, and 20 pct others, such as mill scale and iron sands. Pyrite cinder, a major component in the sinter feed, has been getting finer since 1952, due to the increased grinding required for the improvement of the results in the iron sulfide flotation and to the adoption of FluoSolid roasters in sul-furic acid plants; some fines pass 100-mesh sieve almost completely. Increased use of the fine-sized pyrite cinders in the sinter raw mix resulted in such difficulties as decreased bed permeability, uneven firing conditions, and low yield. In an attempt to study the cause and to find a remedy for this problem, a series of experiments were made, using an 80-kg experimental sintering pan. As a result it was established that, by rolling the fine-sized pyrite cinders into small balls of 10 to 3 mm diam (hereafter called semi-pellets) and mixing them into the sinter raw mix, the bed permeability was improved, the sintering time shortened, and the yield and production rate increased. It is proposed that this new method be called the semi-pellet sintem'ng. In recent years the pelletizing process has taken the spotlight in the agglomeration field for treating fine-sized ores here in Japan as well as in the U.S. and Europe. This process produces pellets suitable for the blast furnace charge as such, and consists of three major operations: fine grinding, balling, and firing. With regard to the firing technique, some problems still appear unsolved. In the semi-pellet sintering, however, several ad- vantages can be claimed: the balling operation is relatively simple because only small-sized balls are shown to be acceptable and the operation can be readily incorporated into the conventional sintering plant, since only balling, not grinding or firing, equipment is needed. Basic test work on the process was initiated in 1954 and favorable results were obtained. Accordingly a pilot plant was built in 1955 and the test work was continued. The semi-pellets thus prepared in the pilot plant were tested further by USing them in the actual sintering pan and their beneficial effects ascertained. In late 1956 a drum-type balling machine (2.4X4 m) was installed and it went into operation in April 1957 in conjunction with the Greenawalt sintering plant (8 pans having dimensions of 7.2 m in length, 3 m in width, and 0.3 m in depth). In October 1958 a cone-type pelletizer, with a 2.2 m diam, and later a disk-type pelletizer were further added in the plant. In the DL sintering plant (2000 tpd), newly built in July, 1960, four disk-type pelletizers (3.2 m diam, 10 tph capacity) were installed. By mixing the semi-pellets thus prepared with the feed, the sintering operation was found to be greatly improved. The results of the basic test work, and the equipment and operation of the semi-pellet sintering operation at the Hirohata Works will be described. ON THE SINTERING CHARACTERISTICS OF FINE SIZED PYRITE CINDERS To ascertain the effect of addition of fine-sized pyrite cinders on the sintering characteristics, a series of measurements on bed permeability was carried out by varying the size distribution of pyrite cinders. The composition of the raw mix used in the tests was fixed at 50 pct pyrite cinder, 20 pct Larap magnetite fines, 30 pct sinter return, and 5 pct coke; only the size distribution of the pyrite cinder was varied. Also the moisture content was changed at each size distribution. The results are given in Fig. 1. For all pyrite cinders tested the bed

Jan 1, 1961

By John Goheen

CONSIDERABLE work has been done in developing a pyrometer to measure the temperature of molten brasses, bronzes, and aluminum in the crucible. On account of the high melting points and the amount of zinc and sulfurous fumes given off from molten brasses, the conditions are somewhat severe for a thermocouple of standard design; but satisfactory results are obtained with a portable pyrometer, 3 ft. (0.9 m.) of connecting lead wire, and a special 5-ft. nickel-nickel chromium thermocouple, composed of rods ¼ in. (6.35 mm.) in diameter. The lower 12 or 24 in., as desired, may be made detachable so that new tips may be connected at little trouble or expense. The portable instrument need not be of the extreme high-resistance type, as the movable parts of the galvanometer of a lower resistance instrument may be better constructed to withstand the continuous handling such an instrument receives. Platinum-platinum rhodium thermocouples, protected with porcelain and graphite tubes, have been used, but the lag in registering the temperature is too great. It has been found that the range of temperature for various brasses is as follows: Red brasses 2200-2250° F. (1205-1234° C.) Yellow brasses 2250-2400° F. (1234-1318° C.) Bronzes 2300-2550° F. (1260-1400° C.)

Jan 11, 1921

By John Mathews

IT is twenty years since the writer made his first molybdenum steels and others were making them commercially five years earlier but the prevailing opinion seems to be that molybdenum steels are new; from time to time the daily press speaks of important discoveries in Europe and intimates that American steel makers have much to learn in regard to alloy steels. The earlier experiments were largely confined to the use of relatively high percentages of molybdenum in tool steels and permanent magnet steels. Recent developments deal with the types of alloy structural steels used for airplane, automobile, and other engineering requirements; in these, the molybdenum content is usually less than 1 per cent. The earlier types generally have been unsuccessful commercially, but the newer types of steels are becoming of increasing importance. The war showed our dependence on foreign sources for alloying metals; molybdenum alone is widely distributed in the United States and seemingly abundant. Many deposits are not now of commercial interest, owing to location and relatively small amount of ore available, but other deposits are being developed and a stable source of supply seems well assured. In tool and magnet steels, it was early found that 1 part of molybdenum was equivalent to from 2 to 2.5 parts of tungsten. The permanent magnet steels investigated by Madame Curie,1 in 1898, contained from 3.36 to 4.05 per cent. molybdenum; in 1902, Dr. E. L. French and the writer thoroughly tested steels containing from 2:0 to 4.0 per cent. These steels gave satisfactory tests for permanence, but were low in residual density and much more sensitive to hardening than the corresponding tungsten products. We discontinued work with them, therefore, and have no advice that such steels have been used commercially here or abroad.

Jan 2, 1921

By P. M. Budge, William L. Fink, Kent R. Van Horn

The investigation of the phase relations of high-purity aluminum-base alloys is a part of the fundamental research program of the laboratories of the Aluminum Company of America. The results of a number of binary and ternary systems have previously been published in the Transactions of this society. The aluminum end of the binary aluminum-titanium system has been studied. This system has received relatively little attention. To the authors' knowledge, there are two previous papers on this subject. E. van Erckelensl determined the constitutional diagram reproduced in Fig. 1. According to this diagram, the liquidus represents the separation of TiA14, (Ti = 30.7 per cent.). He concluded that this is the composition of the compound, because in his work the eutectic horizontal terminated at 30.7 per cent. titanium and the metallographic examinalion of a sample of this composition revealed only one phase. According to the constitutional diagram developed by W. Manchot and A. Leber,² reproduced in Fig. 2 from data given in their article, the liquidus represents the separation of the compound TiA13 (Ti = 37.2 per cent. ). The composition of the compound was derived in a manner similar to that utilized by van Erckelens. Moreover, Manchot and Leber confirmed the composition of the compound by analysis of the constituent left as a residue after dissolving the alloys in weak sodium hydroxide solution. Although these are the only publications describing the constitution of the system, other investigators have studied the composition of the titanium compound. L. WÖhler3 says that there is a compound TiA13 which was later confirmed by W. Manchot and P. Richter4 and by

Jan 1, 1931

By N. L. Svensson

The model developed by Tuylor for the calculation of Polycrystalline yield strength has been applied to the case of an aggregate hawing a preferred orientation. In general this procedure requires the specification of texture by means of weighting factors applied to specific orientations. The problem to which the model has been applied is that of the yield-strength aniso-tropy of cold-rolled aluminum whose rolling texture was described as a combination of (110)[112] and (311) [112] In this case yield-strength anisotropy is defined by the rutio of yield strength measured at an angle 8 to the rolling direction to that measured along the rolling direction. The method of calculation of yield-strength ratio as a function of ? is described and the results show good agreement with experimental values. The orthotropic yield criterion suggested by Hill has been applied to the results and the strain ratio R also calculated as a function of ?. This has been compared with calculations using the method suggested by Elias, Heyer, and Smith which does not exhibit suck good agreement with observation. one deficietlcy of the method presented is that the strain ratios used by are those applying to iso-Irobic materials. The method should therefore be reg-clrded only as a first abbroximation to the prediction of anisotropy. THE problem of calculating the stress-strain characteristics of polycrystalline aggregates from the properties of single crystals has attracted attention for a number of years. The most important contributions to this study have been those due to: Sachs,' Cox and sopwith,2 Taylor,3 Kochendorfer,4 Batdorf and Budiansky,5 Calnan and Clews,6 Bishop and Hill,7,8 Kocks,9 Budiansky, Hashin, and sanders, 10 Kroner,11 Cyzak, Bow, and payne, 12 Budiansky and Wu,13 and Lin.14 While the earlier work has been largely superseded, recent developments tend to support Taylor's solution" within the restriction imposed by his assumptions. The essential features of Taylor's approach were: 1) the material is rigid-plastic; 2) each grain experiences the same strain components as the aggregate as a whole (the problem was that of uniaxial deformation with principal strain components in the ratio 3) all regions of each grain deform uniformly; 4) work hardening occurs equally on all slip systems. While Bishop and Hill7 have generally validated this approach, there has been some criticism offered. Kocks? as pointed out that since multiple slip must occur the single-crystal data must be determined from orientations arranged such that polyslip takes place. Boas and Hargreaves,15 and others, have shown experimentally that the strain distribution within grains is not uniform, the strains in the vicinity of grain boundaries being less than those in the center of the grains. Both of these criticisms can be largely offset by the suitable choice of single-crystal critical shear stress. However, for the problem analyzed below, the critical shear stress is not directly used and, consequently, these criticisms lose their importance. The more recent contributions have attempted to obtain a more complete analysis by considering an elas-toplastic material and considering interactions between grains of differing orientations. Lin14 has considered the early stages of yielding for a polycrystalline aggregate having specific regions of defined slip plane orientations. On the other hand, Budiansky and Wu13 have allowed for these interactions for randomly disposed grain orientations and have calculated the polycrystalline stress-strain curves for crystals exhibiting either elastic-ideally plastic or kinematic hardening characteristics. This work has shown that yielding commences when the macroscopic stress is 2.2 times the critical shear stress for slip in a single crystal (7,). The yield stress-strain curve then rises becoming asymptotic to a value of 3.072 7,. This is close to the value obtained by Bishop and Hill (3.06) in their confirmation of Taylor's method. This, of course, is to be expected since, at large strain values, the elastic strains are negligible and the rigid-plastic model is satisfactory. The results of Budiansky and Wu indicate that the result obtained by Taylor is 7.7 pct high at a plastic strain which is two times the elastic strain at the initiation of yield. By defining the anisotropy in terms of relative values, the ratio of yield strength at orientation ?, to that measured in the rolling direction, the effect of the discrepancy in Taylor's solution is considered to be of lesser consequence. Therefore, it is anticipated that an analysis based on Taylor's solution, which can be quite straightforward, should provide a reasonable estimation of the anisotropy of materials having a preferred orientation texture. OUTLINE OF TAYLOR'S METHOD In fee metals there are four possible slip planes (the octahedral planes) and in each there are three possible slip directions (the edges of the octahedron), that is a total of twelve possible slip systems. von Mises16 has shown that at least five independent slip systems must become operative in each grain of the polycrystalline aggregate in order to preserve continuity of strain. With this geometrical requirement as basis and the assumptions previously listed, Taylor determined the operative slip systems for a number of orientations of the tensile stress axis specified in the unit stereographic triangle. For the ith slip system, the critical shear stress

Jan 1, 1967

NORTH AMERICA Number Members Alaska 31 Canada 302 Mexico 175 Newfoundland 3 United States Alabama 52 Arizona 131 Arkansas 9 California 723 Colorado 184 Connecticut 98 Delaware 19 District of Columbia 133 Florida 16 Georgia 6 Idaho 61 Illinois 241 Indiana 57 Iowa 7 Kansas 32 Kentucky 33

Jan 1, 1932

By Charles R. Cavanaugh, John F. Elliott

The activity of nickel in liquid Pb-iVi alloys which are rich in lead was measured in the temperature region of 700° to 1100°C by means of the galvanic cell: The electrolyte used was stabilized zirconia. Tlze data were correlated using the a function, and a plot of the temperature coefficient aE/aT All subsequent calculations of the thermodynamic properties are based on these two functions. The activity, activity coefficient, and molar properties of mixing of nickel are reported. Nicke1 shows extreme positive deviations frorn ideality while lead shows a very slight positive deviation in the composition range studied The study of the activity of nickel in liquid Pb-Ni alloys reported herein was undertaken to explore the use of stabilized zirconia, an oxygen-ion electrolyte, with liquid-metal electrodes, and to obtain further information on the thermodynamic properties of the liquid binary Pb-Ni system. The cell The reversible electromotive force of the cell results from the difference in the chemical potential of the oxygen at the two electrodes: po, (left) - p~ (right) = -4E5 [I] The chemical potential of oxygen on the right is fixed by the activity of nickel in the solution and pure solid nickel oxide. That on the left is set by pure solid nickel in equilibrium with pure solid NiO. By definition: Since the chemical potential of nickel is related to the chemical potential of oxygen through the equilibrium constant for the formation of NiO from nickel and oxygen gas, the electromotive force of the cell is also expressed In this case, n is 2, E is the reversible potential of the cell, and 5 is Faraday's constant. The work of Kuikkola and wagnerl and Schmalz-reid2 has shown that the stabilized zirconia electrolyte is essentially an ionic conductor at the oxygen levels encountered in the experimental arrangement of the work, i .e., PG > 10-l7 atm. THE EXPERIMENTS The advantage of this type of reversible cell over those using a liquid electrolyte is the simplicity arising because the electrolyte also functions as one of the containing crucibles. A further simplification was the choice of the Ni (sat.)-NiO electrode as the standard. This permitted a ready check on the behavior of the electrolyte, as the potential of the cell must become zero when the right electrode becomes saturated with nickel, either because of a change of temperature or because of the addition of nickel to the electrode. It also permitted the potentials being measured to lie in the most satisfactory experimental range of 0 to 100 mv. Although it was not theoretically necessary, lead was included in the standard electrode as it assured good contact between the electrode and electrolyte. Cell Design. The general arrangement of the experimental cell assembly is shown in Fig. l(a) and the details of the cell itself are contained in Fig. l(b). The anode lead wire on the interior of the cell was connected to a coil of perforated sheet nickel. Within this coil were nickel oxide pellets which were held beneath the surface of the liquid Pb-Ni alloy. A disc of nickel oxide was held at the bottom of the external crucible (alumina) by means of the thermocouple protection tube. The nickel oxide disc and pellets were compressed dry at 10,000 psi and sintered at approximately 1000°C for an hour in air. A major experimental difficulty of reversible electromotive force cells with liquid electrodes is the selection of suitable materials for connecting

Jan 1, 1964

By John Blatchford, William T. Hall

The product obtained by roasting stibnite is likely to contain some unoxidized antimony trisulphide and a mixture of antimony trioxide and antimony tetroxide. It was desired to determine, as accurately as possible, the condition of the antimony as well as the total quantity present. Attempts were made to separate the trisulphide and the two oxides by methods based upon their varying solubilities in different solvents, but no satisfactory results were obtained in this way. It was found, however, that by determining the total antimony content, the antimony present as trioxide, and the antimony present as trisulphide, a good idea of the chemical composition of the roasted product could be obtained. The total antimony was determined by dissolving the sample in concentrated hydrochloric acid, reducing the antimony entirely to the trivalent condition by means of hydriodic acid and eventually titrating the antimony back to the pentavalent condition by means of iodine in the presence of sodium bicarbonate1* The details of the procedure are as follows: Weigh out 0.25 gram of the roasted product into a trapped flask (Fig. I), add 4 grams of powdered tartaric acid, 2 grams of potassium iodide and 40 c.c. of concentrated hydrochloric acid. Boil the solution gently f;r 5 min. and then cool to room temperature by shaking the flask while holding it under running water. Then, very carefully discharge the iodine color by the cautious addition of 0.05-normal sodium thiosulphate solution, adding a little starch toward the last. Nearly neutralize the acid with ammonia solution, but leave the solution distinctly acid. Pour the slightly acid solution into 200 c. c. of water containing an excess of sodium bicarbonate and titrate to a permanent blue color with standard 0.1-normal iodine solution.

Jan 1, 1916

By J. M. Campbell, T. S. Buxton

The most widely used methods of predicting the volumetric properties of gas are based on the principle of corresponding states, which asserts that the compressibility factor is a universal function of reduced temperature and pressure. Previous studies have shown that the acentric factor, as proposed by Pitzer, l is an important addition to reduced pressure and reduced temperature as factors affecting the compressibility factor. Results of this study indicate that, if the pseudocritical temperature and pressure used to determine the reduced conditions are adequately predicted, characterization of natural gas-carbon dioxide mixtures with the acentric factor will allow reliable determination of the compressibility factor. Comparisons of predicted and experimental compressibility factors have shown that the pseudo-critical constant rules of Stewart, Burkhardt and Voo 2 are satisfactory for hydrocarbon mixtures. However, these rules fail to predict the pseduo-critical constants for hydrocarbon-carbon dioxide mixtures. Based on graphically determined pseudocritical temperatures for binary hydrocarbon-carbon dioxide mixtures, a correlation which gives the required correction to the Stewart, Burkhardt and Voo rules was prepared and a compressibility factor prediction technique was proposed. To test the proposed technique, compressibility factors for live mixtures of methane, carbon dioxide and either ethne or propane were experimentally determined at 100, 130 and 160F and pressures up to 7,026 psia. The predicted and experimental compressibility factors for these live mixtures had an average absolute deviation of 0.55 percent. INTRODUCTION Two-parameter generalized correlations based on the principle of corresponding states (PCS) are presently available for reliably predicting the compressibility factor of lean natural gas, i.e., natural gas with low concentrations of hydrocarbons heavier than methane. When these same correlations are used for mixtures of natural gas and carbon dioxide, large deviations between actual and predicted compressibility factors are observed. This study was undertaken to provide a means for accurately predicting the compressibility factor for such mixtures. In the past, two avenues of approach have been employed to extend the applicability of the PCS. The first has been to introduce additional parameters. The second has been to develop combination rules for predicting pseudocritical constants which do not suffer from the limitations of the commonly used molal average constants. In this study, both of these approaches have been considered and employed to arrive at a method for predicting the compressibility factor of mixtures of hydrocarbons and carbon dioxide. SELECTION OF A THIRD PARAMETER Failure of the original PCS to predict the compressibility factor for all pure gases, regardless of their mass, shape or polar moment, has led to the introduction of additional parameters into the PCS. Parameters have been introduced to correct for quantum deviations,3-5 non-spherical or globular shapes6-9 and for polar moments.8-12 In addition to these parameters which are based on some microscopic property and intended to correct for some specific cause of deviation, more general parameters based on some bulk property have also been introduced.1913-16 To use additional parameters to correct for each of the possible causes of deviation among the individual constituents of a gas mixture would require a rather complex form of the PCS. To maintain the PCS in as simple a form as possible, it is more desirable to have a single third parameter which is based on some bulk property influenced by several of the factors causing deviations. The third parameter selected for use in this study is a factor originally proposed by Pitzer.9

By Ursula E. Wolff

Il.lechanica1 twins have been observed in brigsten single crystals of a variety of axial orientations defornzed at room temperature in tension or bending. The twins formed near the final fracture and were up to 3 p thick. The twinning plane was always of the type (113). Twinning at room ternperature occurred only after considerable prior slip. Twins usually preceded fracture and nucleated cracks. The crack surfaces often alternated between a (001) plane and the twin interfaces. Secondary twins could also nucleate from cracks. In the absence of twinning tensile samples failed by shear; twinned samples failed by cleavage. On the assumption that observed sudden load drops in the stress-strain curves are associated with twinning, a critical resolved stress for twinning of 60, 000 to 65, 000 psi was calculated. MeCHANICAL twinning has been observed in iron and iron alloys at low temperature by a number of investigators.'-7 Similarly, for high-purity tungsten, twinning has been reported for deformation temperatures below 211°K.8-10 In W-Re and Mo-Re alloys, 20 pct Re was determined as the lower limit for twin formation at room temperature." Since the twins are generally very narrow, they are usually identified only by etching techniques. The expected (112) habit plane has always been confirmed by angular analysis of the surface traces. Recently, however, a complete identification by X-ray analysis has been performed on twins in a Mo-35 pct Re alloy.12 During an investigation of the deformation charac- teristics of tungsten single crystals, twins were revealed in tensile and bend samples deformed at room temperature. This paper deals with the conditions for such twinning and the relation of twinning to fracture. EXPERIMENTAL PROCEDURE Tungsten single crystals, 1/8 in. in diam, of a variety of axial orientations were grown from un-doped material by four-pass electron-beam zone melting. A representative analysis is given in the following table: From these crqstals, tensile samples with 1 in. gage lengths were made by surface grinding, leaving shoulders for gripping. The diameter after grinding was 0.082 in. The distorted surface layer was then removed by ele1:trolytic polishing which reduced the diameter of the gage length to 0.080 in. Tensile tests were carried out at room temperature in an Instron machine under two different sets of conditions: a) Rigid mounting; strain rate 0.02 in. per in. per min. b) Gimbal mounting; strain rate 0.002 in. per in. per min up to a total strain of approximately 0.2 pct, then 0.01 in. per in. per min to fracture. Stress axis and growth direction coincided in all samples and are subsequently called orientation.

Jan 1, 1962

By John Boardman

THE latest metal-mine accident report available for the United States is that of the Bureau of Mines for the calendar year 1919. Quoting from Table 20, p. 53, of that report, we find that there were 468 men killed, 7 permanently totally disabled, 321 permanently partially disabled, 7848 injured seriously (more than 14 days disability), and 23,330 of 1 to 14 days disability. We have no records to show what the average days lost per case of accident is, but the records for the Anaconda Copper Mining Co. show that, leaving out the fatalities and total permanent disabilities, and counting those in which the lost time was one or more days, the actual days lost due to accidents, for the Butte mines and shops for five years, 1917-1921, were as follows: Accident Statistics, Butte Mines and Shops of A. C. M. Co. Rate Shifts Days Lost Year Accidents Total Shifts 10,000 Shifts Days Lost Per Acci-dent 1917 2,661 3,169,720 8.395 26,734 10.05 1918 2,765 3,545,149 7.799 39,199 14.17 1919 1,381 1,853,143 7.452 22,797 16.50 1920 1,376 1,879,410 7.321 20,164 14.65 1921 376 776,461 4.842 8,287 22.03 Total... 8,559 11,223,883 7.625 117,981 13.80 In order to place an economic value. on this loss, we will assume that all the 468 fatalities and the 7 total permanently disabled in the United States were com-pensated for at the rate which applies in the State of Montana, that is, $5000 each, and that the 8169 serious accidents in the United States were compensated for at an average of $70 per case, thus bringing the estimated compensation paid by metal-mining companies in the United States to the enormous total of $2,946,830 for the year 1919. The figure of $70 per case was obtained by dividing the total amount paid by metal-mining companies under Plan No. 1 of the Montana Compensation Law, for the first five years of its operation, by the total number of serious accidents for those years.

Jan 9, 1922

By Leah L. Naugle, H. G. Landau, H. H. Lowry

EVIDENCE has been accumulating in recent years, in part from the work of the Coal Research Laboratory, that coals belong to a family of natural polymers and that even in complex reactions the differences between coals are quantitative and not qualitative. This point of view leads to the expectation that if a series of coals were subjected to a closely controlled set of experimental conditions the results obtained should be related to the chemical analyses of the individual coals. The data accumulated over the past 10 years by the Bureau of Mines in its "Survey of Coke-, Gas-, and By-Product-Making Properties of American Coals," in what has come to be recognized as the Bureau of Mines-American Gas Association (BM-AGA) carbonization assay test,1-12 offer an unusual opportunity to check this conclusion. The present paper reports an analysis of the data on the first go coals and coal blends-including coals numbered I to 55b, inclusive -which have been carbonized according to a standard procedure at intervals of 100°C. from 500° to 1100° in either or both 13 or I8-in. cylindrical retorts." In Table I are given the name of the seam from which the sample was obtained, the analytical data used, and the reference to the original publication of the Bureau of Mines. The coals range in fixed carbon from 46.2 to 79.0 per cent, in volatile matter from 15.4 to 41.3 per cent, in ash; from 2.1 to 15.9 per cent, in moisture from o.8 to 19.7 per cent, and in total sulphur from 0.40 to 4.44 per cent; therefore the entire gamut of bituminous coals is represented. The petrographic nature of the individual coals is not considered in the following analysis, although both "normal" bright coals and splint coals are included in the samples studied. For information on the petrography of the coals and for further information characterizing the coals the original papers should be consulted. Although the coals that are included extend over the whole range of bituminous coals, they do not cover this range entirely adequately. In particular, only 13 of the go coals have moisture contents greater than 3 per cent. This concentration at low moisture values means that the effect of moisture, which is an important factor, cannot be determined with as much certainty as would be desirable. All the coals were not tested at every temperature and in both retort sizes. Only the first 30 coals were tested at 1100°, and only about 50 at the other temperatures, except at 900°, where nearly all of them were included. In the accompanying tables the actual number of observations entering into each correlation is given. In this study equations are given for calculating analyses, yields, and properties of coke and by-products from the coal analyses. To decide whether these equations are satisfactory it is necessary to know the accuracy with which these quantities were measured in the assay tests.

Jan 1, 1941