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By E. P. Polushkin, Henry L. Shuldener

This paper describes the results of microscopic examination of a series of brass pipes removed from apartment and office buildings in New York City, adjacent localities on Long Island, and Philadelphia. They were selected as typical of approximately four hundred pipe specimens obtained over a period of five years during an investigation of corrosion in hot-water installations. A part of the investigation is reported in this paper and includes a brief history of the pipes, a description of their inside surface and microstructure, and a study of the effects of corrosion, with particular reference to the structural aspects of local and selective dezincification. Although the bibliography on the corrosion of brass pipes is quite extensive, it refers almost entirely to corrosion in sea water. The authors believe that their examination of this series of pipes, which had been subjected to the corrosive action of fresh water for various lengths of time, may throw some additional light on the problem of corrosion. Pipes Examined The pipes were made by different manufacturers and their sizes range from 3/4 in. to 4 in. nominal inside diameter, the majority being within I to 2 in. They can be divided into two groups according to chemical composition: (I) with a copper content of 60 to 62 per cent and (2) with a copper content of 65 to 68 per cent. The first group (pipes made of Muntz metal) comprises 22 pipes and the second (pipes made of high brass) comprises 18 pipes. The pipes had been in service in various locations in the hot-water systems of the buildings involved. Some were taken from horizontal lines in the basement, some from overhead distributors and some from vertical risers. The distance, in terms of feet of pipe, of the specimens from the hot-water generator was no less than 75 ft. and often IOO to 300 ft. In the majority of cases the water-heating equipment was provided with a regulator to limit the temperature of the hot water supply. The normal range of temperature in pipe systems of this kind is Ioo° to 160°F. Water Supples The average chemical composition of the water supplies carried by the pipes is shown in Table I. In evaluating the corrosiveness of a natural water, four factors are considered of prime importance: namely, hardness, alkalinity, pH and silica content. The waters listed in Table 1 are characterized by relatively low hardness, 10, alkalinity, low pH and low silica content. The waters of lower pH and higher CO2 content are more corrosive. A characteristic of all of these waters is that they do not deposit a protective mineral coating as do waters with high bicarbonate of lime content, which would be reflected

Jan 1, 1945

By E. T. Turkdogan, Klaus Schwerdtfeger

OelSEN and Maetz1 detected some 20 years ago the existence of a miscibility gap in iron oxide-CaO-P2O5 slags melted in iron crucibles at about 1400°C. Because of the importance of this system for the dephos-phorization of steel in the basic Bessemer process, equilibria between liquid iron and selected iron oxide-CaO-P2Q slags have been measured since by numerous investigators.2-5 When in equilibrium with metallic iron, the iron oxide of the slag is present mainly as FeO. In connection with oxygen-blowing steelmaking processes, it is useful to know the phase relations in the slag system at higher oxygen pressure, when major parts of the iron oxide are present as Fe2O3. This problem was investigated by Turkdogan and Bills7 by equilibrating the oxide mixtures contained in platinum crucibles with CO2-CO mixtures at 1550°C. It was found that increasing the Fe2O3 content decreases the composition range of the miscibility gap strongly so that the miscibility gap has almost disappeared at pco2/pco = 75. This result was refuted by the careful work of Olette et a1.,''' who equilibrated their slags with controlled Ha-H2-Ar gas mixtures. Their equilibrium measurements, at 1600°C and at oxygen pressures of 5 x 10"* and 10"5 atm, showed that the oxidation state of the iron has almost no influence on the formation of the miscibility gap. The present experiments were undertaken to check the previous results of Turkdogan and Bills. The experiments were performed at 1625°C in the strongly oxidizing atmosphere of air (PO2 = 0.20 atm) for which no experimental data are available. About 10 g of slag were melted in platinum crucibles and held at constant temperature for 1 hr. After equilibration, the crucible was rapidly pulled out of the furnace and cooled in air. The platinum crucible was removed from the sample. The two slag layers were carefully separated with a small diamond disc, and the surface of the top layer, which may have changed its oxidation state during cooling, was removed. The slags were crushed and analyzed chemically for CaO, P2O5, Fe2+, and Fetotal. The starting mixtures were prepared by sintering the desired amounts of reagent-grade 2CaO . P2O5 - H2O, CaCO3, and Fe2O3. Sintering and subsequent crushing were done three times to ensure homogenization. Molybdenum wire resistance heating was used. The furnace was provided with a recrystallized alumina reaction tube which was left open to air at the top. The temperature was controlled electronically. The reported temperature was measured with a Pt/Pt-10 pct Rh thermocouple and is estimated to be accurate within +5°C. The composition of the equilibrated melts is given in Table I. For the graphical illustration of these quaternary slags the type of projection suggested by Trömel and Fritze10 was used. In this representation, Fig. 1, the composition point of a mixture within the tetrahedron Fe2O3-CaO-P2O5-FeO is projected into the Fe2O3-CaO-P2O5, triangle (triangle I) so that the direction of projection is parallel to the side FeO-Fe2O3, and into the triangle Fe2O3-P2O,-Fe0 (triangle 11) so that the direction of projection is parallel to the side CaO-P2O5, of the tetrahedron. The projected point has the coordinates wt pct CaO, wt pct P205, and wt pct (FeO + Fe2O3) in triangle I and wt pct FeO, wt pct Fe2O3, and wt pct (CaO + PzO5) in triangle 11. Both triangles are turned into the same plane around the Fe203-P20, side of the tetrahedron. An illustration of the projection of a quaternary point in the present system is shown in Fig. 1. The advantage of this type of projection is that all four components for an equilibrium curve can be read directly from the diagram. The present results are shown graphically in Fig. 2. The curves depicting the miscibility gap are dashed in parts where no experimental points were obtained. The composition range covered by the miscibility gap

Jan 1, 1968

By A. Mitchell

An approximate phase diagram has been developed for the CaF2-CaC2 system, indicating a eutectic point at 1240°C, Ncac2 = 0.13, and no detectable solid solution in either phase. The liquidus line is shown to correspond to a simple c22- ion in solution. A thermo-chemical study of&apos; the reaction between carbon-saturated Ni-Ca alloys and CaC2-CaF2 liquids indicates that lhe Raoullian activity coefficient of CaC2 in dilute solution in Cap2 al 1500°C lies between 8 and 10. Some effects of the stabilily of Cap2-CaC2 solutions at high temperatures on electroslag remelting praclice are outlined. THE alkaline earth acetylides. MIIC2, have a reasonably high thermochemical stability at high temperature in the solid state,&apos; with the exception of magnesium, which forms an unstable acetylide at low temperatures (-500°C) and a carbide, Mg2C3, in the range 700&apos; to 1000°C. The acetylides of calcium and barium have been shown to have limited solubility in their respective chlorides,&apos; and further these solutions contain the acetylide as a C: ion.&apos; The equivalent magnesium solutions have not been studied. Although calcium "carbide" is used as a desulfuriz-ing reagent in steelmaking. and is possibly present as an acetylide-oxide phase in very basic electric arc practice slags, the acetylide ion appears to be substantially unstable in a silicate slag.* As a conse- *This instability arises from equilibria in the reaction: CaC2 + CO = (Ca0) + 3C where the low intrinsic solubility of CaC2 in silicate lattice, and the low activity of CaO in a silicate solution where CaO/Si02 < 1, combine to give a very small equilibrium concentration of CaC2 in solution in such silicate slags at temperatures in the region of I 500°c, even under carbon-saturated conditions. Under highly basic conditions, a liquid CaO-CaC2 phase may separate from the silicate system quence of this, the possibility that reactions involving CaC2 in silicate solutions are of importance to general steelmaking practice is remote. However, in operations involving a slag primarily based on a halide, or alkaline earth oxide, we must take into account the possibility that CaC2 will appear in quantities sufficient to significantly affect both the chemical and physical properties of the slag. The work outlined below presents a study of the CaF2-CaC2 system intended to provide sufficient data to allow an estimate of the importance of this system to electroslag remelting and welding practice. However, we should indicate at this point that there will be other processes, e.g., heat treatment, flux cleaning of castings, fused salt electrolysis, and so forth, where alkaline-earth halide fluxes are in contact with carbon, graphite, or carbides, and where halide-acetylide solutions must be taken into account. EXPERIMENTAL 1) Structural Studies. In view of the difficulty ex-perienced in handling CaC2 prepared from calcium turnings and propane gas at 700°C, it was decided to use solutions prepared directly in the equilibration apparatus, Fig. 1. The starting materials were: a) Ni-Ca-C alloy, prepared by adding calcium to liquid nickel held under calcium fluoride in an induction-heated graphite crucible; b) calcium fluoride, prepared by fusing calcium fluoride powder (British Drug House "EXTRA PURE") calcium fluoride in an induction-heated graphite crucible, in air, followed by electrolysis between graphite electrodes at 1 amp cm-2 density, for 10&apos; coulombs per g CaF2. This procedure decomposes the CaO produced by hydrolysis during the fusion step, replacing it by CaC2; Ca2+ + 2e-Ca*(l) Ca*(l) + 2C(gr)-(CaC2)caF2 O2- -2e-O*(g) O*(g) +C(gr)-CO(g) This results in a composition of between 2 and 5 wt pct CaC2 in CaF2. Fifty grams (in lumps) of this material were placed in a graphite crucible, together with Ni-Ca-C alloy (averaging 20 wt pct Ca), and the equilibration apparatus assembled. The alloy reacted with the crucible at high temperature to give CaC2, which dissolved in the calcium fluoride solution to give the desired composition. Cooling curves were plotted manually for these liquids, with rapid stirring and CaF2 seeding to minimize supercooling, and using a Pt/Pt 13 Rh thermocouple calibrated on the freezing points of nickel and copper. This gave a reproducibility of ±0.l°C. and an absolute accuracy of the thermocouple of ±l°C. An example curve is shown in Fig. 2, with the CaF2 end of the binary system in Fig. 3. The CaF2-CaC2 ingots were crushed, under dry nitrogen, and sampled for chemical analysis and X-ray examination. Analytical details are given in the Appendix. Powder diffraction data indicated that the only phases present in all samples examined were calcium fluoride and tetragonal (Types I and 111) calcium acetylide,4 with no evidence of solid solutions or compound formation. 2) Thermochemical Studies. The apparatus used to obtain activity data on CaC2 in these systems is shown in Fig. 4. It consists of an arrangement whereby the graphite crucible and its contents (CaF2-CaC2. Ni-Ca-C) can be rapidly cooled without exposure to air. Trial experiments to determine an equilibration time by ap-

Jan 1, 1969

[A discussion suggested by the paper of Mr. James Gsyley on " The Development of American Blast-Furnaces," read at the New York meeting of the Iron and Steel Institute, October, 1890, and reprinted from the Journal of that Society in Bans. A. I. M. E., xix., 932.1 (Cleveland Meeting, June, 1891.) [Kote by the SecretaRy.—The three following contributions to this discussion were communicated by letter to the Secretary of the Iron and Steel Institute, and were received by me too late for insertion in vol. xix. of the Transactions.] FRed. W. Gordon, Philadelphia, Pa.: Mr. Gayley&apos;s paper calls our attention to the very expensive blunder hitherto made in blowing too much wind in a given size of furnace. It was quite evident from an analysis of blast-furnace operations that the work we are doing in America is anything but creditable. We were consuming fully 1000 pounds of coke more than is necessary for each ton of iron made, and were hammering the linings of our furnaces out in a very short time, and nothing but the very high price of pig-iron would stand the drain. It had long been my pet scheme to gradually reduce the quantity of air, at the same time increasing the burden to the maximum and decreasing the limestone, and determining, if possible, the fuel economy which might be reached consistently with the maximum production of the furnace. After the success of the Isabella furnace at Pittsburgh, which was remodelled in 1880, the North Chicago Rolling Mill Company had

Jan 1, 1892

By C. G. Dunn

According to a recently suggested effect of silicon on the re recrystallization textures of high-purity Fe-Si alloys with (111)[112] type rolling textures, the recrystallization texture for a rolled (110)[001] oriented iron crystal probably should be entirely different from that of a (110)[001] oriented 3 pct Si-Fe crystal. Comparative studies of iron and 3 pct Si-Fe crystals, however, show that both have (110)[Ool] recrystallization textures when the rolling textures are the (111)[112] type after reductions in thickness of about 70 pct. Qualitatively the results from the iron crystal are like those of polycrystalline high-purity 3 pct Si-Fe and not like polycrys-talline high-purity iron. The large effect previously noted probably involves unknown impurities or processing variables rather than silicon itself. Some problems on experimental and analytical procedure for a spherical X-ray specimen, which was machined from a laminated composite of sheet specimens, are treated in the Appendix. A possible strong effect of silicon on the textures produced in cold-rolled high-purity Fe-Si (HPFe-Si) alloys during primary recrystallization and normal grain growth was suggested in a recent paper.&apos; All the textures were far from the random-orientation type, but that of iron, or of Fe-Si alloys of low silicon composition, was entirely different from the texture of 3 pct Si-Fe. The same effect was noted for the textures obtained prior to normal grain growth, i.e., for primary recrystallization.2 It is the main purpose of the present paper to provide some clarification of this silicon effect. All the HPFe-Si alloys from zero to 3 pct Si, which were rolled by two or more stages separated by anneals, developed (111)[112] type rolling textures.2 Thus, there was no effect of silicon on the rolling textures. Earlier, Gensamer and Mehl3 also found no effect of silicon on the rolling textures of Fe-Si alloys; they obtained the Kurdjum.ow and Sachs (K-S) rolling texture for iron,4 which is characterized as the three ideal components: (100)[011], (112)[li0], and (111)[112]. There is a difference between the HPFe-Si multiple-stage rolling texture and the K-S single-stage rolling texture, but this is a variable processing effect. Of interest here is the fact that the recrystallization textures from (111) [llZ] type rolling textures were different depending on the amount of silicon in the alloy. There was a relatively strong (110) [001] component in the recrystallization texture of HP 3 pct Si-Fe5,8,2 but no such component in HP 0.6 pct Si-Fe, for example; the recrystallization texture for the latter was two (111) [110] type components and a (111) fiber component 1,2 Several publications have shown that a strong (110) [001] recrystallization texture is derivable from a (111) [112] type rolling texture for 3 pct Si-Fe crystals reduced in thickness by about 70 pct.7-10 Furthermore it appears that the strongest of these (110) [001] recrystallization textures occurred when the orientation of the crystal prior to rolling was (110) [001].7 Barrett and evensoon11 found that the rolling texture of a (110)[001] oriented iron crystal was (111) [llj]. Accordingly, it seemed desirable to determine whether a (110) [001] oriented iron crystal, upon rolling and annealing, would behave like the 3 pct Si-Fe crystal (or the polycrystalline HP 3 pct Si-Fe) and thus produce a (110) [001] recrystallization texture contrary to the suggested silicon effect, or would behave like the polycry stalline HP iron or HP 0.6 pct Si-Fe and thus produce (lll) [110] type components in agreement with a silicon effect. Briefly, the idea here involves the use of more precisely defined textures to obtain if possible better control of important variables that affect the recrystallization process. PROCEDURE A (110) oriented crystal of Ferrovac "E" iron (99.9 pct pure) was prepared in sheet form 0.080 in. thick with the [001] direction parallel to the long dimension of the specimen.&apos;&apos; This crystal was etched to 0.073 in. thickness (to remove some small included grains) and then was cold rolled in a 6-in.-diam mill to a final thickness of 0.022 in. The rolling was unidirectional except for an inadvertent reversal at 0.061 in. thickness. At this thickness, and also at 0.040 in., the rolling was interrupted for transmission Laue photographs. Molybdenum Ka-radiation filtered with zirconium was used in a transmission method1&apos; to obtain the cold-rolled (110) pole figure. The sample was a 0.002-in.-thick section taken from the central region of the 0.022-in.-thick cold-rolled crystal. For the primary recrystallization study, cold-rolled samples were etched from 0.022 to 0.021 in. thick and annealed in hydrogen at 850°C. Primary recrystallization to a fine-grained structure, Fig. 1, was obtained in a 5-min anneal. Eleven sheets after

Jan 1, 1963

By d&apos, K. Mukherjee, C. R. Antonio, R. J. Maciag, G. J. Fischer

Tensile data indicate that over the range of strain rates 10-5 to 10-1 sec-1 and in the temperature range 298° to 743°K the flow stress at a given temperature may be expressed as: C0 = Cem where m changes abruptly at a critical strain rate of 10-2 sec-1. The Zener-Hollomon parameter was tested and found to be invalid except at temperatures exceeding 700° K. Values of AH calculated for temperatures above 700°K ranged from 30 to 47.5 kcal per g-mole. ThE flow characteristics of aluminum and aluminum alloys as a function of temperature and strain rate have been of interest to various experimenters for many years. Trozera et al.1 determined tensile flow curves for pure aluminum and concluded that the combined effect of temperature and strain rate on the flow stress could be related using the Zener-Hollomon parameter. More recently, Hockett2 proposed a relationship between compressive flow stress, temperature, and true strain rate which could be represented by a surface. Holt et al.3 studied strain rate effects on flow stress in a number of aluminum alloys at room temperature. It was determined that there is a critical strain rate above which a strain rate effect is observed. It was also reported that the strain rate sensitivity was significant in aluminum alloys in the "0" condition only. In a recent review paper McQueen4 has considered a number of mathematical expressions which have been used to describe the relationship between stress, strain rate, and temperature. These expressions have been applied to the flow characteristics of a number of different metals and alloys including aluminum. In the present work the strain rate sensitivity of 7075-0 aluminum was determined in the temperature range of 298° to 743°K. The tensile flow stress at 0.2 pct offset was obtained over a nominal strain rate range of 10-5 to 10-1 sec-1. EXPERIMENTAL Threaded tensile specimens were cut from a single heat of 7075-T6 aluminum. The composition of this heat is given in Table I. The test bars had a gage section 1.5 in. long by 0.250 in. diam and conformed to ASTM specification E-8-57T. After machining, the bars were annealed at 413° ± 10°C for 2 hr. They were then cooled to 260°C in 3 hr, and finally air cooled to room temperature. This treatment is commonly used to produce the "0" condition. Load-time curves at constant crosshead speeds were obtained at various temperatures using an Instron testing machine. Crosshead speeds ranged from 0.002 to 40 in. per min. A three-zone resistance tube furnace was used for the elevated-temperature tests. Temperatures were measured at three points along the gage length by means of suitably placed thermocouples. Each tensile bar was held at temperature for 30 min prior to testing and the maximum temperature variation along the gage length was kept below 1°C. In all, 275 samples were tested and each data point plotted is an average of at least two tests. In many cases the point represents up to six tests. RESULTS AND DISCUSSION Values of the flow stress at 0.2 pct offset at six different temperatures are plotted vs strain rate on log-log coordinates in Fig. 1. Over discrete ranges of strain rate, the data for each temperature fit the expression:

Jan 1, 1969

By S. G. Cupschalk, F. A. Dahlman, J. J. Wert

Studies have been undertaken to determine the indicidual effects of particle size, degree of long-range ovder, antiphase domain size, and root mean square stran on the microhardness and yield strength of ordered alloys. Dnta have been analyzed for Cu3Pt initzally ordered to a value of 0.82 and after deformations of 1 and 6 pct. It was observed that deformation fleatly reduced the degree of long-range order. Furtherrnore, wztkin this range of relatively small deforntntlons, the average particle size changed very little while the antiphase domain size was greatly reduced. Smultaneosly, the mcrohardness changed by a factor of two durzng the deforrtation process. PREVIOUS studies have reported some of the effects of cold work on the broadening of X-ray diffraction peaks. These investigations were performed on powder and wire samples representing both ordered and disordered states; i.e., the specimens were initially studied in a severly cold-worked condition. By comparing the difference in line shape between the annealed and cold-worked peaks, fundamental information was obtained concerning particle size, strain distribution in different crystallographic directions, degree of long-range order, and change in antiphase domain size. Considerable theoretical work has been done concerning the analysis of diffraction data obtained from cold-worked metals. Stokes&apos; expressed the change in diffraction profiles in terms of Fourier coefficients. Much of the work in this area has been summarized by warren2 in an extensive review article concerning the analysis of plastic deformation by X-ray diffraction. Cohen and Bever3 applied these techniques in studying the effects of cold work on alloy systems exhibiting long-range order. They utilized the Fourier coefficients of fundamental peaks in conjunction with those of the superlattice peaks to determine the change in antiphase domain size. Little work of this nature has been reported for ordered systems that have undergone small degrees of plastic deformation. The purpose of this investiga-tion was to determine the effects of small deformations in such a material with respect to particle size, strain distribution in various crystallographic directions, antiphase domain size, degree of long-range order, and hardness. EXPERIMENTAL PROCEDURE CusPt was used for the initial investigation since the order-disorder transformation takes place with- out a change in crystal structure. The transformation is readily detectable via X-ray diffraction techniques due to the large difference in the scattering factors of copper and platinum. Additionally, the alloy is relatively low melting (approximately 1300°C) and is easily deformable in both the ordered and disordered states. 1) Specimen Preparation and Cold Working. A 100-g, 12-in. diam., cylindrical specimen of Cu3Pt was prepared by melting and casting 99.99 pct pure Cu and Pt i.n vacuo. Prior to any mechanical working, the material was homogenized in a vacuum for 60 hr at 100O0C, and surface defects were removed by machining to a depth of approximately 116 of an in. The material was then cold-rolled, with an intermediate anneal, into a strip approximately 12 in. wide by 14 in. thick. Straightening and flattening removed another 0.025 in. from the thickness. After a recrystallization treatment at 750°C for 30 min, the specimen was slow-cooled from 55OoC, at the rate of 6°C per hr, down to 150°C to induce superlattice formation. This treatment yielded an ASTM grain size of 7 and a degree of long-range order equal to 0.83 0.06. After obtaining X-ray and Knoop hardness data, the sample was cold-rolled approximately 0.75 pct in one pass through a hand-operated jewelers&apos; mill. X-ray and hardness data were again obtained and the specimen was reduced an additional 5.41 pct in a single pass through the mill. 2) X-Ray Measurements. The specimen was examined in the ordered condition and after the two degrees of cold working previously mentioned using a General Electric XRD-5 unit equipped with a spectrometer and scintillation counter. Using Mo-Ka radiation with a zirconium filter, six orders of the 100 reflection were obtained. It was anticipated that point counting would be necessary for an accurate determination of the low-intensity peaks and tails: however, it was demonstrated that, by using a scanning speed of 0.2 deg per min and the appropriate time constant, the recorded data were sufficiently accurate. Thus, for ease of experimental procedure, all peaks were recorded on chart paper. Specimen position in the holder was considered to be insignificant after making a series of measurements of the same peak area in different positions with respect to the beam. Since peak overlapping did occur at high values of 20, it was necessary to separate the peaks graphically prior to analyzing the data in order to minimize this source of error. The peak tails were also carefully drawn to obtain the best possible data. Fourier coefficients of the line profiles were calculated on an IBM 7072 computer, and graphical meth-ods2j3 were employed in analyzing the results. For this type of calculation, in which the line profile is represented by intensities taken at set intervals, the intervals selected must be sufficiently small to give an accurate representation of the line profile. It was decided that for 20 = 0.02 deg the line profiles were

Jan 1, 1967

By P. D. Merica, H. Scott, R. G. Waltenberg

The remarkable phenomena exhibited by the aluminum alloy known as duralumin were discovered during the years 1903—1911 by A. Wilm1,2 and have been described by him and by others. 3, 4,5.6 The unusual feature of this alloy is the fact, as was shown by Wilm, that it can be hardened quite appreciably by quenching from tempera-

Jan 1, 1921

By P. Greenfield, P. A. Beck

RECENT work by J. Darby, Jr. in this laboratory has shown that the reported vanadium-rich limit of the s phase in the Co-V system at 1200°C is in error. The appearance of a second phase in s actually is restricted to alloys containing over 68 atomic pct V. The error in the original value is due apparently to a reaction that takes place along the numerous cracks in the s specimens between the alloy and the impurities present in the He + 8 pct H atmosphere in the annealing furnace. Such a reaction and the consequent appearance of a second phase can be suppressed if the alloys are sealed under vacuum in Vycor tubing. The new value of 68 atomic pct V for the vana-dium-rich limit of the s phase in the Co-V system effects slightly the s compositions calculated from average values of N, and N,. for various s phases. The standard deviation between experimental mean compositions and those calculated from the assumption that s is characterized by a constant number of 3d + 4s electrons per atom (N,), is slightly reduced from 9.1 to 8.8 pct. The maximum divergence for the V-Mn s phase is reduced from 15.5 to 14 atomic pct. The standard deviation calculated from constant electron vacancy numbers given by N.. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2(Fe) + 1.71(Co) + 1.6(Ni) is now greatly reduced, as the maximum divergence for this correlation previously occurred in the V-Co system. This maximum divergence is reduced from 7.6 to 2.3 pct, and the standard deviation for all s- phases is reduced from 4.1 to only 2.9 pct. The correlation for electron vacancy numbers given by N. 5.66 (V when with Ni or Co) + 4.88 (V when with Mn or Fe) + 4.66 (Cr + Mn) + 3.3 (Mn) + 2.66 (Fe) + 1.71 (Co) + 0.61 (Ni) is made slightly worse, and the standard deviation increases from 2.8 to 3.9 pct. These changes, however, do not affect the conclusions of the paper.&apos; The deviation between calculated and experimental s compositions is much less for either one of the electron vacancy correlations than for the correlation with the number of 3d + 4s electrons.

Jan 1, 1955

By Charles H. Fulton

There are comparatively few accurate data on the melting-or the freezing-point temperature of metallurgical slags, or on related physical phenomena, such as fluidity near the melting-point, specific heat, latent heat, etc. With the exception of the work of H. 0. Hofman,&apos; and some older work by R. Akerman, P. Gredt, and H. M. Howe, no information is available that is of direct interest to the metallurgist. Hofman&apos;s valuable work is the only one that refers to slags produced in the metallurgy of copper and lead. The classic work of J. H. L. Vogt,2 who views slags from the standpoint of physical mixtures (solutions in which the entities are minerals), has opened up a new field in the study of slags, and has placed the investigation of such properties as melting-temperatures, etc., on a rational basis. The recent work of A. L. Day, E. T. Allen, and W. I?. White, of the Carnegie Institution, at Washington, and of European investigators3 on certain systems of silicate minerals confirms the value of the investigation of silicate series from this standpoint, and it is my aim to apply this method to metallurgical slags, in order to gain exact data of value in metallurgy. The work recorded in the present paper is the result of an investigation of reverberatory-furnace slags made for a Western smelting company to determine exactly the influence of change in composition, within comparatively narrow limits, on the melting-point. For a general discussion concerning the mineralogical character of slags and the principles on which this investigation is based, reference should be made to other work: for the subject is too large to be stated in this paper, except very briefly in the following outline:

Jan 1, 1913

By Jacob Reese

longer and tougher. In the worst case I have observed, viz., two inches difference in circumference, this difference in hardoess, as observed from the cutting, was more marked than in the other cases. Tires are always grouped in sets by the manufactrlrers fiorn their knowledge of the chenlical camposit,ion of the steel, with an attempt to get those in one set which have the same degree of hardness, so that the wear shall be equal all around ; they succeed pretty well on the average, but I have been noting the exceptioiis. Jacob Reese, PittsHukQh, Pa. : I have been very much interested in the reading and discusion of Dr. Dudley&apos;s paper. As far as it selates to the data of work performed by the rails, and the determination of their physical and chemical properties, I have nothing but commendation of Dr. Dildley to express, as the investigation covered a greater range, and was performed with more care in detail, than any similar work which has come under my notice. But I beg leave to differ with Dr. Dudley in his conclusions. What are the factors of hardness? Are they not carbon, silicon, phosphorus, and manganese? Now it is an untlisputed fact among iuetallurgiml experts that pure carbon and pure iron make the best steel of all degrees of carburieation, and for all purposes. While carbon hardens, it also strengthens the metal, but silicon, phosphorus, and manganese, in hardening, make the metal also brittle, and are injarious in any amount. Carbon should be called a strengthener; and I claim that a steel rail made hard with carbon, with the other three hardeners absent or reduced to a minimum, will carry a greater tonnage than any of Dr. Dudley&apos;s soft rails. But until the basic process is put into operation in this country we cannot expect to produce Bessemer or open-hearth steel without the presence of silicon, phosphorus, and manganese, in consitlerable quautities, aod I greatly donht the possibility of reducing the perceutage of any of them by the prment practice without seriously diminishing the output, and correspondingly increasing the net cost of production; which is an important question, since the increased life of the rail may be more than balanced by its increased cost. I think that the soft rails performed a greater amount of work, because they contained a less amorlllt of silicon, phosphorus, and wangatwe (britlkrcr, if I may so term them), and that carbon does wt reduce the wearing capacity of rails. I believe that a rail made by the baqic process, with silicon, phosphorus, and manganese reduced to a minimum, and containing 0.60 carbon, will be stronger

Jan 1, 1881

By R. W. Hunt

The old plan was to increase every part of a rail much in the same proportion. But each part should be in proportion to what it ha.; to do. The head should be deep in proportion to tile amount. of traffic and the lowness of the rate of interest on its cost. The body need only he strong enough to carry the head after it is well worn down, and that deperlds on the weight of the machinery, and in the case of steel has little to do with the volume of traffic, except SO far as that affects weight of machinery. Ad on most railroad systems, the same niacliinery is used on main lines with heavy traffic, and bra11ct:es with light, I suggested in 1874 that each systern adopt the same body of rail for both, and make the head deeper on the main lines, shallower on the branches. This plan was adopted on the Pennsylvania Railroad. Bandberg seems to recognize this in his patterns of 1878. E. W. HUNT, TRoy, N. Y.: Again Dr. Dudley preaents to our cousideration a series of most carefully conductetl experiments, and ~llile I fully appreciate the labor and thought this work has cost him, I must still hesitate to accept his deductiono. This paper dilliirs from the previous one in that it denls esclrieively with the wearing qualitiei. of steel rails. Dr. Dudley gives his reason for this change in the following statement: " With the improvement in maintenance of way which has characterized the Pennsylvania Railroad during the last five or six yearn, the remova1 of rails from the track from the first two of these causes (i. e., broken and crushel), has, if I am right, quite notably diminished. This certainly is true with regard to broken rails. And if, as time advances, the number of crushed rails shall diminish, both because of the continued improvement in maintenance of way before referred to, and because, owing to improved and better methods at the steel works, there are fewer crushed rails caused by physical defects in the steel, the question of the wearing capacity of steel rails obviously becomes the allimportant one." Certainly the condition of the roadhd has much to do with mils brealring, crushing, and wearing. If the Pennsylvania and other railroads have done and are doing their part, Dr. Dudley oourteously admits that the steel works have performed part of theirs. But as far as I am informed, the formulas which they have used have been and are still quite wide of the one he continues to recommend. The rails which are not breaking or crushing to so great an extent as formerly, contain higher percentages of both carbon and manganese.

Jan 1, 1881

By J. R. Cahoon, H. W. Paxton

The possibility of using unidirectionally solidified, two-phase alloys as an approximation to fiber composite materials is investigated. The short-term me.chanical properties and failure modes of unidirectionully solidified A1 (rich)-Cu alloys containing ap -Proximately 0, 17.5, and 27.7 vol pct of 0 phase &apos;fibers" are determined at temperatures from 25" to 500" and compared with those obtained for conventionul SAP alloys. In a previous publication,&apos; hereafter referred to as I, the possibility of understanding some of the room-temperature mechanical properties of unidirectionally solidified castings was explored. For Al(rich)-Cu and Al(rich)-Mg two-phase alloys over a substantial range of compositions, the yield and ultimate strengths and common ductility measures were very adequately predicted from the principles of fiber strengthening4 and the analysis of ductility outlined by Gurland and Plateau." The results obtained in I suggest the possibility of using unidirectionally solidified, two-phase alloys to simulate fiber composite materials where the inter-dendritic second phase or constituent acts as the reinforcing material. Recent attempts concerning the fabrication of fiber conlposites have concentrated on producing composites with a good bond between fiber and matrix and with very long fibers so that their maximum contribution to the strength of the composite may be realized. However, these objectives are difficult to attain in practice and present fabrication processes are either extremely laborious or costly.13 The slow, unidirectional solidification of eutectics has received considerable attention as a method for producing composite materials. 5,6 This method can fulfill both of the above objectives but it is currently laborious, expensive, and has the additional disadvantage that the volume fraction of reinforcing phase cannot be easily varied. On the other hand, unidirectionally solidified, two-phase alloys, also with a good bond between the phases, are relatively easy to make and the volume fraction of reinforcing "fibers" can be easily varied by changing the average composition of the alloy. The disadvantage of the cast alloys is that the mechanical effectiveness of the "elongated interdendritic reinforcements" (EIR)* may be reduced due to their rela- tively short lengths, the w factor in Eq. [2] of I. However, if the EIR have a high strength their contribution can be considerable. For composite materials containing discontinuous cylindrical fibers of various lengths the ultimate strength is given by1 where it is assumed that the composite fractures when the fibers fail. In Eq. [I], a, is the stress in the matrix just prior to failure of the composite, Vf is the total volume fraction of fiber reinforcing constituent, Vf(l+) is the volume fraction of fibers whose lengths exceed the critical length, I,, which is defined as the shortest length of fiber in which the stress can build up sufficiently to break the fiber. af is the fracture strength of the fiber material, w is a factor accounting for the discontinuity of those fibers whose lengths exceed I,, 1-/d is the average aspect ratio of those fibers whose lengths are shorter than I,, and t is the shear stress in the matrix at the fiber-matrix interface. The factor w is dependent on the length of the fibers and also on whether deformation of the matrix occurs plastically or elastically. However, for a given length of fiber, w is smaller when elastic deformation of the matrix is assumed.&apos; It is of interest to consider the properties of simple unidirectionally solidified, two-phase alloys at elevated temperatures in view of the possibility of using suitable modifications for high temperature service. Knowledge of the creep behavior of these materials is still rudimentary (although under active investigation) and the present paper concerns itself with short time tensile properties of some alloys similar to those investigated in I (i.e., unidirectionally solidified Al(rich)-Cu alloys). Unidirectionally solidified alloys containing 5.6, 17, and 23 wt pct Cu were tested parallel to the direction of solidification at temperatures from 25" to 500°C. In the present investigation, the alloys were homogenized for 2 days at 535°C giving a matrix of homogeneous a phase (5.2 wt pct Cu) and an interdendritic constituent (EIR) which was completely Q phase (53 wt pct Cu). EXPERIMENTAL Alloys of nominal composition 5.6, 17, and 23 wt pct Cu (containing approximately 0, 17.5, and 27.7 vol pct 8 phase, respectively, after homogenization at 535°C) were prepared by melting 1200 g of A1 (99.99 pct) in a high purity graphite crucible and adding the appropriate amount of freshly cleaned copper chips (99.9 pct). The molten alloy (at 700°C) was poured into a preheated graphite mold (also at 700°C) and the ingot unidirectionally solidified by impinging water on the steel baseplate of the mold. The alloy was degassed immediately

Jan 1, 1970

By Charles M. Rolker

The Mariposa estate, a grant made by the Mexican Government to Juan 13. Alvarado, during the time when California was still under the dominion of Mexico, was purchased in 1847 by J. C. Fremont, and the United States patent issued to him in 1856. By sale, or its equivalent, money advanced, the property came into the hands of the Mariposa Company, June 25th, 1863, and through a varied existence of work and temporary inactivity, has as yet been kept as an undivided property, and rests at present with the Mariposa Land and Mining Company of California. I pass over this period of 15 years without giving the history of the ups and downs of the estate, partly because it is familiar to many, and also because I think in such a case this paper would assume too much the character of a narrative. The estate is situated in Mariposa County, California, about 170 miles southeast of San Francisco. It begins in lat. 37&apos; 26&apos; 38&apos;&apos; north, and long. 119&apos; 55&apos; west, and runs 6 miles north; thence 69 miles west; thence 5 miles northwesterly towards the Merced River; thence 84 miles southerly; thence 3 miles easterly; thence 1 mile southerly; thence 2 miles easterly; thence 2 miles southerly; thence 2 miles easterly; thence 1 mile southerly; thence 2 miles easterly; thence 1 mile northerly, and thence 2 miles easterly to the place of the beginning; embracing 44,387 acres (70 sq. miles) more or less. To describe this vast estate in detail as to its full geology, its numerous quartz veins, its many facilities to exploit them and work them by cheap methods, would lead me further than I intend to go at present, and I will content myself to describe the latest workings of the company and its immediate field of operations. As long ago as 1860 the late Dr. Adelberg advised the running of an adit from the northwestern edge of the estate at Benton Mills 011 the Mereed River. His object was to undercut the deepest workings of the then paying mines on the estate—the Pine Tree and Josephine. Following this advice, the tunnel known as "River Tunnel " was commenced. Its entrance is in S. 5, T. 4, s. R. 17 E. It is run in

Jan 1, 1879

By W. D. Robertson

A considerable quantity of experimental data is available on the effect of time, temperature, work-hardening and composition on the mechanical properties and corrosion resistance of aluminum alloys. There is, however, little unity of purpose or generality in most of the studies and, because the number of variables is large, the results often are not applicable to the problems that arise in practice. Furthermore, the customary expression of the effect of different variables as separate curves or as three-dimensional diagrams with time, temperature and the dependent variables as coordinates, renders the task of selecting the optimum time and temperature of precipitation treatment, with respect to their simultaneous but unequal effect on the various properties, exceedingly difficult. The introduction of precipitation treatments to raise the yield strength of 24S-type alloys has created a need for a method of correlating and summarizing the effect of time and temperature on the mechanical properties and susceptibility to intercrystalline corrosion. Correlation is particularly desirable because the choice of time and temperature is of necessity a compromise to achieve the best possible combination of properties, and the optimum conditions cannot be accurately specified unless the data are in a form in which the alternatives can be readily compared. Therefore, the work described here was undertaken to find a common relationship that would be capable of expressing the effect of precipitation time and temperature on the various properties and by means of which the relative effects could be correlated and their interpretation facilitated. REVIEW OF PREVIOUS WORK In connection with an investigation of the interrelation of age-hardening and creep performance of nickel-silicon-copper alloys, Jenkins and Bucknall1 demonstrated that the time required to attain maximum hardness and tensile strength could be expressed by a relationship of the form: t = K. 10m/T (I) where t is the time in hours and T the temperature of aging, expressed in degrees absolute, and m and K are constants. They also pointed out that this expression is analogous to that which describes the change of the diffusion coefficient D with temperature; namely, D = Ae-Q/RT (2) Later, Cohen used this relationship in studies of the mechanism of age-hardening of a silver- rich copper alloy2 and of duralumin. 3

Jan 1, 1945

By R. J. Franklin, G. W. Beckman, D. Warren, E. Both, J. F. Libsch

BINARY and ternary alloys of iron, nickel and cobalt respond to annealing in a magnetic field by a characteristic change in the shape of their hysteresis 100p.l,2 An increase in retentivity and a decrease in coercive force produced by the magnetic treatment cause the hysteresis loop to approach the appearance of a rectangle. Materials with a rectangular hysteresis loop have made possible the contact-rectifier³ and have greatly improved the performance of pulse transformers4 and magnetic amplifiers." In the best material presently available for these applications, a 50 pct nickel-iron alloy," the desired characteristics are achieved by aligning the preferred crystallographic directions of magnetization along the rolling direction of the tape. The objective of the present study has been to produce rectangular hysteresis characteristics in materials with inherently high saturation. Iron-cobalt alloys, exhibiting saturation values up to 24,000 gausses&apos; appeared to offer promise for the magnetic annealing technique, because they remain magnetic to very high temperatures,8 exhibit favorable magnetostriction properties: and show zero crystal energy at 42 pct cobalt.10 Among the ternary iron-cobalt-nickel alloys,7,11 response to heat treatment in a magnetic field is unfortunately limited to alloys having rather low saturation values.&apos; It appeared interesting nevertheless, to study a series of compositions connecting the optimum composition (50/50) of the binary iron-cobalt system with the "Perminvar" composition (30 pct Fe, 25 pct Co, and 45 pct Ni). Very recently, R. Smoluchowski and R. W. Turner," have shown that under certain circumstances magnetic annealing can produce oriented recrystallization. A combination of this technique with the domain orientation utilized in the present study might well result in further improvements. The advantages of the powder metallurgy technique in preparing magnetic alloys for study have

Jan 1, 1951

By William Metcalf

William Metcalf, Pittsburgh, Pa. : In rising to discuss Dr. Dadley&apos;s paper, I feel somewhat as I did at the Baltimore meeting —that a "crucible" man has no right to interfere in a "Bessenier" discussion; yet having read the paper very carefully, I feel impelled to say something, for two reasons: First, because I believe Dr. Dudley is entirely on the right and having undertaken and partly accomplished a great work, he .is entitled to the help of all who have experience in these matters; and second, because the data given force me to colicur in Captain Jones&apos;s opinion that the analyses are incomplete, since they ignore sulphur, copper, nitrogen, and possibly other injurious elements. In an experience of fourteen years, and with probably more than a hontlwl tests, we have never found the chemistry and the of crucible steel to disagree. If in any cave a disagreement tins sp- . peared, it has been our invariable custom to go over all our physirtal testa with great care, and if we found no error, then to refer the matter back to the cherubt, who has invariably found some unexjmted element to account for the trouble. It is only just to the chemist to say here, that ordinarily be is only expected to determine phosphorus, silicon, sulphnr. Generally the metals, with the exception of manganese, are not looked for, although a watch is usually kept for copper and arsenic. Further, in most cases we have found our own work more liable to be faulty than the chemist&apos;s. Having arrived then at such a degree of experience that we can preJict the analysis from our tests, or our tests from the analysis, with almost absolute certainty, I can see no reason why the same results map not be attained in the Bessemer practice. But two things are essential, neither of which we have here; first, cornplete analyses; and second, a record of the nature of the blow, the heat at which the ingots were bloomed, and the mile finished,—in short, a complete history of the This latter is quite as essential as accurate and complete analyses. Dr. Duclley ignores sulphur and copper on fair enough grounds commercially speaking, bnt when he announces so gmve a conclusion as he has reached, in a scientific way, the omission of any elementn that, may affect the conclusion is hardly justifiable. His diEerenvcs of phosphorus units, which I milst term units of rottenness 83 fr os phosphorus is concerned, and which I am sorry be did not llama wnits of alloys,—are very small, and if eulphur and copper hod been inclurlid they might havo upset hie conclusions sitogether, The

Jan 1, 1881

By D. D. Pollock, D. I. Finch

Relationships between the compositions of specially prepared manganin-type alloys and some of their electrical properties have been established. Empirical equations, based upon the electronic configurations of the alloying elements, are given which describe the resistivity, temperature coefficient, peak temperature, and thermoelectric power of Cu-Mn-Ni-Fe alloys at approximately room temperature. Calculations based upon these relationships are correlated with experimental data. SECURING suitable alloys for the construction of stable resistors, for use in precise electrical measuring devices, has been important ever since the art of electrical measurement was begun. German silver, Pt-Ag, and Platinoid are examples of some of the alloys in early use. These early alloys were un- satisfactory for one or more of the following reasons: l—insufficient stability of electrical properties with time, 2—poor reproducibility of electrical characteristics from melt to melt, 3—excessive temperature coefficients of resistance, and 4—excessive cost. Weston introduced the Cu-Mn-Fe and Cu-Mn-Ni-Fe alloys of the type now generally known as manganins. His patents are believed to represent the first disclosure of any alloy with a negative temperature coefficient of resistance. After this work, the German company, Isabellenhutte, in conjunction with Feussner and St. Lindeck, produced alloys of

Jan 1, 1957

By J. Chipman, G. G. Hatch

One of the important functions of the iron blast furnace is the desulphur-ization of pig iron before it enters the steelmaking furnaces. However, the increasing concentrations of sulphur in the metallurgical coke, source of approximately 90 pct of the sulphur present in the blast furnace charge, and demands for higher rates of production within recent years have increased the need for greater desulphurization within the iron blast furnace. Furnace operators are beginning to look for desulphurizing agents other than blast furnace slag to accomplish the desired degree of desulphurization. A considerable amount of work has been done on desulphurization outside the furnace with soda ash, calcium carbide and various synthetic slags. Whether the desulphurization of pig iron is accomplished wholly inside the furnace or partly inside and the remainder outside, will be determined by the economics involved. Regardless of which is the case, it is believed that it is necessary to have a better understanding of the physical chemistry of desulphurization by blast furnace slags. To this end, it is the object of the present investigation to attempt what is believed to be the first equilibrium study of the distribution of sulphur between liquid pig iron and a wide range of blast furnace slag compositions. Review of Literature There is a considerable amount of information in the literature concerning the desulphurizing power of iron blast furnace slags, the solubility of various sulphides in the slags, and the effect on desulphurization of temperature, of elements dissolved in the liquid iron, and of viscosity. However, there is nothing to indicate that the equilibrium distribution of sulphur between liquid iron saturated with carbon and iron blast furnace slags has been studied experimentally. Wentrupl has made probably the most detailed study of the desulphurization of pig iron to date. He considered that there are three distinct aspects involved, namely: 1. Desulphurization within the blast furnace (by lime and manganese). 2. Subsequent desulphurization by manganese. 3. The effect of subsidiary reactions on the desulphurization by manganese. The experimental work carried out by Wentrup was devoted mainly to obtaining a better understanding of how desulphurization by manganese was accomplished in the mixer and the ladle. Particular attention was given to the part played by carbon, silicon, and phosphorus associated with manganese in the iron, and the effect of temperature on desulphurization. The experimental results indicated that desulphurization by manganese is purely a process of crystallization of manganese sulphide. The addition of silicon to iron melts containing 3.5 pct carbon and less than 0.5 pct manganese had no noticeable effect on desulphurization, but with 1-2 pct manganese the silicon additions improved the desulphurization. Additions of phosphorus also resulted in improved desulphurizati011 by manganese, but the effect was not as marked as in the case of silicon. It was also found that desulphurization by manganese was further improved by lowering the temperature. In order to explain desulphurization inside the blast furnace, Wentrup considered the system iron, sulphur, calcium, oxygen, manganese. (silicon). The distribution of sulphur between the metal and slag was represented by the following equation: (SS) _ (S)Fe + (S)Ca + (S)Mn .... [S] = [s] [1] The parentheses and the brackets represent the equilibrium concentrations in weight per cent of the slag and metal constituents, respectively. Since FeS D (FeS) _ (FeS) (S)Fe LfeS - [FeS] [S] [2] (CaO) + S e (FeO) + (S)Ca _ (FeO)(S)Ca. (S)Ca _ (CaO) Kl = (CaO)[S] [S] ~K1(FeO) [3] Mn + S D (S)Mn (S)Mn (S)Mn K&apos; = [MnpT "1ST = *lIMnJ !4) Substitution of Eq 2, 3, and 4 into Eq 1 resulted in if = L- + *> (Sol + K^ (S) [51 Eq 5 was used to calcu1;lte -f^j and [S] at 1480°C for slags containing 30-50 pct lime, 0.1-2.5 pct iron oxide, 0-26 pct silica, 2 pct sulphur and iron analyzing 1.5 pct manganese. The value for LFaB at 1480°C was found to be equal to 4.5, based on the experimental work of Bardenheuer and Geller.2 The results of the calculations are shown in Table 1. Although the slags are hypothetical and do not represent the range of compositions found in ordinary blast furnace practice, the calculations indicate that lime is effective in controlling desulphurization only if the iron oxide and silica contents of the slag are kept low. Schenck3 did not claim K1 to be a true equilibrium constant, but an empirical value which varied with the silica content of the slag.

Jan 1, 1950

By I. Lowthian Bell

THERE has been probably no improvement introduced into the manufacture of iron which created more surprise in the minds of practical smelters and of scientific men than Neilson&apos;s discovery of the hot blast. In 1829, Messrs. Dunlop & Co. consumed at the Clyde Works, near Glasgow, nearly 79 tons of coal to make a ton of pig iron, of which about 20 cwts. was employed under the boilers of the blowing engines, leaving nearly 7 tons for the consumption of the furnace itself. In the year 1833, by heating the air to 612&apos; F. (322&apos; C.), they redoccd the 79 tons to 3 tons by the mere burning of 8 cwts. of coal in the apparatus for raising the blast to this temperature. The statenlent just given is strictly true in a commercial sense, but when we come to consider the question as one of physical science, it is necessary to eliminate some of the conditions which conduced to so extraordinary a result. Anterior to Neilson&apos;s time the fuel employed in smelting iron was coke, and it was supposed at that period, erroneously, however, that coal in its raw state, when burned with cold air, was totsally unfit for the purpose in question. This mineral, as it was obtained from the Lanarkshire coal-field, contained about 35 per cent. of volatile matter, but the process of charring it was performed in so unskilful a manner that instead of receiving 88 cwts. of coke from 135 cwts. of coal, 60 cwts. only was the product of the operation. Again, the reduced colisumption of carbon in the furnace itself was accompanied by a corresponding diminution of blast, and this was followed by an economy of half a ton in engine coal. After making a proper allowance, however, for all these collateral circumstances, we are within the mark when we admit that in actual coke, which is really the form the fuel has to assume before it is burnt in the blast-furnace, not less than 30 cwts. was saved by heating the blast to 615° F. (322° C.). This unexpected economy, be it remembered, was obtained by the combustion of the 8 cwts. of coal, somewhat wastefully applied in the hot-air apparatus. Numerous have been the opirlions advanced by different authorities in the scientific world to account for the apparent anomaly, bat none,