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By A. U. Seybolt

DURING the course of experiments involving oxygen equilibrations with a high-purity Pd-5 at. pct Rh alloy, the appearance of a subscale was noted. Most of the heat treatments in a pure oxygen atmosphere were performed at 900°C. The presence of the subscale was noted when the oxygen partial pressure was in excess of approximately 95 mm, up to 1 atm, the highest pressure used. According to available thermodynamic information' on the free energy of formation of Rh2O3 (the only reliably reported solid oxide of rhodium), this oxide should not be stable under these conditions, nor, of course, any oxide of palladium. Extraction of the subscale from the matrix was affected by treatment with aqua regia, and the resulting X-ray diffraction powder pattern is shown in Table I. This pattern is not that of Rh2O3, nor that of any known rhodium or palladium oxide. It can be indexed on a hexagonal lattice with a. = 5.22Å and co = 6.0Å. In addition to this unknown material, there was a weak Rh2O3 pattern. An X-ray fluorescence analysis of the powder gave 3214 palladium counts per sec and 5381 rhodium counts per sec, thus indicating the likelihood of a double oxide of palladium and rhodium. In view of the fact that the above result was obtained on a single sample, it is perhaps best not to insist upon the above ratio of about 0.6, but possibly to tentatively assume 0.5 or 1/1. The small amount of Rh2O3 in the X-ray pattern might have occurred on cooling, and it seems possible that the double oxide, below some temperature level, is not as stable as Rh2O3. To examine this point, some of the extracted double oxide was heated on a sheet of pure palladium in air at 900°C, and allowed to furnace-cool over a period of several hours. The X-ray diffraction pattern of the powder showed approximately the same intensity of Rh2O3 and the "hexagonal" oxide as before, but, in addition, a rather faint pattern of another crystalline species made its appearance. This finding again suggests partial transformation of the major (double) oxide to other oxides on cooling from 900°C. Application of the phase rule shows that only one equilibrium oxide (subscale) could have been present at temperature. Vacuum-fusion, oxygen analysis of the extracted subscale showed 7.7 ± 0.7 pct O. Combining this information with that of the X-ray fluorescence analysis suggests the formula PdRhO. This compound should have an oxygen content of 7.07 pct, which is within the range of error of the oxygen analysis. However, until a more careful stoichiometric study is made, it is suggested that the formula be written

Jan 1, 1965

By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson' obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock' used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

By Roscoe C. Clark

A study of the effect of various corrosive waters on five different types of cements indicated that those cements containing less than 5 per cent tricalcium aluminate were the most resistant to corrosion. INTRODUCTION Oil field experience indicates that some formation waters are excessively corrosive to some cements. A study has been made to determine the most corrosive waters and the relative resistance of various types of cement to these corrosive waters. PROCEDURE This study of the corrosion of cement was limited to an evaluation of the effect of various corrosive waters on five different types of cements. A determination was made of the types of cements which offer the greatest resistance to corrosion and of the chemical contents of waters found to be the most destructive to cements. The laboratory tests were conducted by immersing small cylinders of 20 samples of set cement in various corrosive waters. The initial mixing of most of the cement slurries was done using Tulsa tap water as the mixing water; however, a few of the slurries were mixed using a sulfate water as the mixing water. When the 20 samples had been immersed for a period of nine months, they were removed from their corrosive baths, inspected and photographed. The field tests were conducted by placing ten cement specimens, each contained in a screen wire thimble, in the gas anchors of insert pumps in wells in six different fields. The specimens were observed whenever it was necessary to pull the pumps and were returned to the 1aboratory when deterioration had reached a serious state. EXPERIMENTAL RESULTS In both the field and laboratory tests the resistance of the different cements to corrosion was determined by the condition of the samples and the number of samples of each that were in good condition at the end of the immersion period. Table I lists the various cements tested in the order of their resistance to corrosion with the most resistant at the top and the least resistance at the bottom. An analysis of Table I reveals that the upper half of the table predominates in slow set and sulphate resisting cement.: (low 3CAO.A12O3 content) while in the lower half the port-land and high early strength cements are in the majority. Of the last two the high early strength cements appear to offer less resistance to sulfate water corrosion. An investigation of the composition of the cements listed in Table I indicated that as a general rule the cements containing less than five per cent tricalcium aluminate will exhibit the greatest resistance to corrosion. The destructive action of various corrosive waters was compared by listing the waters in the order of those containing the largest number of samples that failed completely. These ratings are presented in Table II with the most corrosive waters listed first and the least corrosive last. Figs. 1 and 2 show the end views of cement samples which had been immersed in the baths of five per cent MgSO, water and the five per cent Na2SO4 water respectively in the laboratory. These .pictures are representative of the results obtained and present a pictorial evaluation of the corrosive resistance of various types of cements.

Jan 1, 1950

By W. M. Brown

SEQUACHEE Valley includes portions of the counties of Marion, Sequachee, Bledsoe and Cumberland. It extends in a general direction parallel with the Great Valley of East Tennessee, some 75 miles northward from the Alabama state line. It is separated from the Valley of East Tennessee by a mountain arm about a dozen miles wide, known as Wallen's or Walden's Ridge. The genesis of the valley, geologically speaking, is simple. It is an erosion-valley along the axis of an anticlinal. The point of the wedge remains in a row of low "saw-tooth" hills, running up the center of the valley. These hills are of Lower Silurian age, and consist of Trenton limestone, covered and protected in some measure by chert. Walls of Carboniferous age form the inclosing mountains on either side; whilst a magnificent arch of Hudson River, Niagara, Hamilton and Subcarboniferous strata closes the valley at the

Jan 1, 1886

By Frederick A. Mumpton

For more than 200 years zeolites have been familiar minerals to geologists and mining engineers as minor, but ubiquitous constituents in vugs and fractures of most basalt and traprock formations. More than 35 different species have been recognized including several, such as chabazite, erionite, mordenite, and faujasite, whose adsorption properties rival those of many synthetic molecular sieves. Igneous occurrences of this type have never been mined on a commercial scale; they are generally small and low grade, and they commonly contain as many as four zeolite minerals, along with small quantities of calcite, quartz, and other silicate minerals. Their economic beneficiation to monomineralic zeolite products has also not been achieved and, for the most part, industrial applications of zeolites have relied primarily on synthetic molecular sieves that were crystallized from hydrous aluminosilicate gels. During the middle 1950s, when Union Carbide Corp. and other groups were developing processes and markets for their fledgling synthetic zeolite businesses, natural zeolites

Jan 1, 1975

SINCE I have told you of the distillation of waters and the extraction of oils from things-all ingenious and useful processes-I wish to continue to speak of the arts. I am reminded that I first wish to write down for you the discourse that I made to you on another occasion a few days ago concerning the operation of a mint, so that if you have lost it from your memory (and this would not be surprising since you have had no practice in it) you may repossess it if you should need to practice it or even to talk about it, and if you find yourself in this activity it may not be new to you. I told you, as I believe you will remember and so again I repeat, that a very great and constant diligence is required by one who wishes to operate a mint well, or to have it operated, because it has many parts which it is necessary for anyone who enters this work to understand very well; indeed, if he wishes that all the work of his helpers be done well, he will have to do it himself. And if it were possible, he should have a hundred hands and a hundred eyes together, and at the same time should be in different places, because some loss often occurs in what is handled because of the carelessness of the workers or because of their little real trustworthiness. It is understood that such things require great hard labors and many kinds of knowledge. The material handled in this work is most often either gold or silver all ready to be spent, and these things are very attractive to those who handle them. In addition to being made into pieces of money likely to disappear, it is very easy to lose, and whatever part is lacking for any reason whatever [132v] brings detriment and loss to the patron since it is a thing of value. Therefore, in short, anyone who wishes to exercise this art well, without being fraudulent therein, must watch the weights with all care because the essence of this art is naught but the division of a quantity of weight into many exactly defined pieces and the alloying of gold by carats and of silver by leghe, exactly established in accordance with what the prince grants you as remedy.* If through negligence you exceed in perfection

Jan 1, 1942

By James R. Holden, Frederick E. Wang

Through both single-crystal and powder X-ray diffraction methods, ten A6B23-type compounds have been confirmed to exist between lanthanides (A) (plus scandium and yttrium) and manganese (B); A = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The formation of a compound of this type is shown to he extremely atomic size-sensitive; hence it can be classified as a "size-factorH compound. The "enveloping effect", a geometrical consideration observed in its crystal structure, is proposed as the reason for the A6B23-type compound being size-sensitive. The approximate ideal geometrical ratio of the radii R/r is 1.31 while experimentally A6B23-type compounds have a radius ratio lying within the range 1.2 to 1.4. FLORIO t al.' characterized the structure of Th6MnZ3 as fcc, space group Fm3m, with 116 atoms in the unit cell. Since then, a number of isotypic binary compounds, and recently Gd n,,' have been confirmed to exist. The fact that strontium and barium form A6Bz3-type compounds with magnesium strongly suggested the possible existence of Ba6Liz3. However, investigation3 showed the compound Ba6LiZ3 to be absent. Since both strontium and barium are group 11-a elements and are therefore "open metals",6 the nonexistence of Ba6LiZ3 can hardly be explained satisfactorily by valence-electron considerations. On the other hand, the consistent atomic-radius ratio, (R/r),* observed for the known A6Bz3-type compounds,3 strongly suggests that the formation of compounds of this type is atomic size-sensitive. Therefore, one is tempted to explain the nonexistence of Ba6LiZ3 entirely on the basis of the atomic-size difference between strontium and barium. However, this approach is not entirely without objection. Atoms are not rigid spheres and are known to vary in size within certain limits.7 Since the atomic-radius difference between strontium and barium (0.07 to 0.09A) is within these limits, it is reasonable to assume that the size difference would have a negligible effect on the formation of Ba6LiZ3. This view is further supported by the fact that the radius ratio, R/r, in other known "size-factor" compounds is observed to range widely—for example, from 1.08 to 1.45 for ABz-type compounds (C15, MgCuz type)' and from 1.37 to 1.58 for AB5-type compounds (D2d, CaZn5 type).g The present investigation was undertaken in order to find a more satisfactory explanation for the non-existence of Ba6LiZ3 and, consequently, a better understanding of the nature of the A6Bz3-type compound. The primary objectives are to confirm the previous conclusion3 that the A6B23-type compound is indeed a "size-factor" compound and subsequently to determine the atomic-radius ratio range in which the A6Bz3-type compound can exist. In order to achieve these objectives, stoichiometric A6Bz3 alloys, where manganese (B) was alloyed with various lanthanide elements (A), were selected for investigation. The atomic-radius ratios of lanthanide elements with manganese range from 1.26 for Lu/~n to 1.46 for Eu/Mn. This radius ratio range includes and exceeds the range of all previously reported A6Bz3-type compounds—1.32 for Th/Mn' through 1.38 for Sr/Li. Furthermore, the atomic-size difference between successive elements of the lanthanide series in order of atomic number) is of the order of 0.01A (europium and ytterbium are exceptions). The series of lanthanon-manganese alloy systems is ideally suited to a precise determination of the limits of allowable atomic-radius ratio for A6Bz3-type compound formation. EXPERIMENTAL PROCEDURE The lanthanide metals, in ingot form, supplied by Michigan Chemical Corp. (St. Louis, Mich.) and Nuclear Corp. of America (Burbank, Calif.), were guaranteed by the suppliers to be at least 99.9 wt pct pure (traces of silicon, calcium, and other minor constituents present on occasion, not to be more than 0.05 wt pct) as shown by spectrographic analysis. Manganese metal, in polycrystalline form, was redistilled from the commercial, chemically pure grade and was analyzed to be at least 99.95 wt pct pure. In all cases, the atom ratio between the two elements in each charge was A (rare-earth meta1):B (manganese) = 6:23 and a constant weight, 3 g, of

Jan 1, 1965

By C. T. Eddy, R. W. Drier

The conductivity of copper wire is of prime importance to the electrical industry and consequently to the copper refiner and wire manufacturer. Annealed copper wire has a higher conductivity than hard-drawn wire, but, on the other hand, its tensile strength is lower. In an attempt to explain the reasons for these changes in properry. or at least to study the conditions existing in these two types of copper wire, the experiments described here were carried on in the Department of Metallurgy of the Michigan College of Mining and Technology This is only a partial and preliminary report on some of the work done to date on a research program of which the object is an intensive study of copper. It is offered with the hope that, though it is not an exposition of the most rigorous of conclusions, the general trend of inferences which may be drawn will be of value and interest. Effect of Direction of Drawing In 1928 some work was done on hard-drawn copper wires to determine whether wire drawn in a continuous machine (that is, all in one direction) would have a different structure from wire that had a reversal in direction at some stage of the drawing process. The diffraction spectra obtained indicated that as the position of the wire rayed approached the core, a preferential crystal orientation existed, and that the closer to the core the more preferred was the orientation. The data obtained partly corroborated the work done by Schmidt and Wassermanl and by Clark.2 Samples Used in Following Investigation The samples selected for use in both the diffraction work and the resistivity measurements were taken from Nos. 6, 8, 10 and 12 gage

Jan 1, 1930

By V. Balasubarmanian, Rajendra Kumar

ISOTHERMAL formation of martensite in a copper-aluminum-nickel alloy was previously reported by Hull and Garwood.' In the present work an attempt has been made to investigate some of the character- istics of the formation of isothermal martensite in binary copper-aluminum alloys containing 14.00 and 14.50 pct Al, respectively. Chill-cast alloys were prepared from OFHC copper and aluminum of greater than 99.5 pct purity. They were homogenized for 24 hr at 950° C. Polished samples were soaked at 1000°C and quenched in water to retain the p phase untransformed; martensite did not form during the quench. The surface was then repolished for isothermal microscopic studies at room temperature. The salient features of the martensitic transformation in copper-aluminum alloys observed in this investigation are: a) The transformation progresses (i) by nuclea-tion at new sites and (ii) by simultaneous slow isothermal growth of existing martensite plates. Slow isothermal growth of martensite has previously been observed by Holden2 in an uranium-chromium alloy and by Hull and Garwood in copper-aluminum-nickel alloy. b) Martensite plates nucleate preferentially at the pin holes formed during the casting of the specimen, Fig. 1. c) Some of the martensite plates pass right through other plates lying in their path, Fig. 1. d) Martensite plates cross grain boundaries without any change in the direction of growth. e) An irregular network of markings, Fig. 2, appears simultaneously with the formation of martensite. It was less prominent in the case of 14.5 pct alloy. The markings may arise due to spontaneous deformation under the lattice strains of the martensitic transformation. Crossing of martensite plates was first observed by Kulin and cohen3 when a high-nickel steel was cooled to 77°K. They suggested that the rapidly advancing plates atquire considerable kinetic energy and strike the obstructing plate with a momentum so as to nucleate the process on the other side of the plate. This, however, fails to explain the present observation where the slow isothermally growing martensite plates cross each other. Such plates would not possess large momentum to bodily displace the obstructing plate. Fig. 1 shows the martensite plates crossing each other without body displacements. This should be contrasted with Fig. 3 of Kulin and Cohen's paper where crossing of plates is accompanied by shearing or body displacements of the plates. The present observations can, how-

Jan 1, 1961

By Jesse O. Betterton

In the Parkes process of lead refining, after desilverization has been completed by means of zinc additions, there will remain in the lead from 0.5 to 0.6 per cent zinc. At this stage in the refining practically all impurities are reduced to refined lead specifications except zinc and antimony. All excess of copper and nearly all the arsenic goes out with the silver. Silver remaining should not exceed 0.1 oz. per ton. It thus remains only to remove zinc and antimony to produce refined lead. The older practice was to complete refining by means of oxidation processes in reverberatory furnaces. Essentially this consisted of heating the lead to 1200' to 1300" I?. and allowing it to come in contact with a considerable excess of air passing through the furnace, or accomplish the same result by blowing the lead with steam by means of pipes introduced for that purpose, at the same time allowing air to enter the furnace. Usually some procedure involving alternate oxidation and reduction with fine coal or coke was employed in order to reduce the weight of dross or skim finally removed from the furnace. This practice had many elements of weakness in that the main flour of lead, after the preceding expensive operations had been performed, and the whole refining process nearly completed, was subjected to an operation at a comparatively high temperature, which involved much lead loss if the furnaces were not on bags, and the production of 3 to 5 per cent of the weight of the lead as dross or skim, which had to be resmelted and the lead either refined or produced as antimonial lead. In addition, the operating expense of the process was a considerable item. The process of dezincing with chlorine was developed as a substitute for the foregoing described oxidation process, and finally resulted in such advantages as nearly equal operating costs, a practical elimination of the lead loss, and the direct production of a very valuable byproduct, zinc chloride, that may be sold as such or retreated for its zinc and chlorine contents, both of which can be reused in the refining processes. Essentially this process consists of circulating the lead by means of a pump in a kettle through a closed reaction cylinder, gaseous chlorine entering the reaction cylinder with the stream of lead from the pump. Molten zinc chloride is thus produced and is discharged together with

Jan 1, 1937

By Will Mitchell, T. G. Kirkland, C. L. Sollenberger

R. S. Handy (Santa Rosa, Calif.)—It would be interesting to learn the comparative results of treating the Korean scheelite ore described in this paper according to the following procedure: I—Follow the procedure described in the paper to the recovery of the sulphides by flotation. 2—Dilute the residue from the sulphide flotation strongly with water and disperse the contained colloids by adding a mixture of 75 pct sodium silicate and 25 pct quebracho to dispersion point. 3— Settle the dispersed pulp and decant the supernatant colloids. 4—-Dilute, settle, and decant the pulp until the settled residue is crystalline. Not over 10 pct of the tungsten minerals should follow the colloids. 5—Treat the settled residue by flotation, having established the proper pH. Oleic acid homogenized with cresylic acid or kerosene is more selective for scheelite than is oleic acid alone. (The recovery of the contained tungsten minerals should be practically complete in this operation.) 6—Deflocculate the tungsten concentrate from step 5 with the same dispersion agents as in step 2 and treat the deflocculated pulp by gravity. The minerals that tend to float with scheelite are generally of low specific gravity and the separation is efficient. The heavier contaminants, such as pyrrhotite and magnetite can be removed magnetically, leaving a practically pure scheelite. E. J. Pryor (Imperial College of Science and Technology, London)—It occurred to me that instead of using temperature as a differentiating control, more precision might be obtained with a reagent of a type we developed here for the flotation of high grade fluorspar in cold pulps. This reagent, which is manufactured on a modest scale in England, is based on oleic acid, which has been modified by our patented process to ensure complete stable dispersion at any desired concentration in water. It thus becomes possible to utilise unimolecular layers with good selectivity. In the fluorspar flotation for which we developed it, it is possible to hold a tight control on depressing quebracho for the calcite without substantial loss of flu-orite, and recovery exceeding 99 pct is not uncommon in the mill where it is in use, even under wintry conditions. No attempt has been made yet to extend the use of the reagent, as we have not completely overcome

Jan 1, 1952

I BELIEVE that my work would surely be host a seed without fit and that I would fail in that cause which disposed me to satisfy your request to write and form this work [75] if while laboring on it I did not tell you of the art of casting, since it is a necessary means to very many ends. I realize even more that I must tell as much as seems necessary since I have already demonstrated the methods of recognizing the natures and locations of the metals, of smelting and reducing them to their ultimate perfection, and finally have taught you to make their associations and alloys. It is especially necessary since this art and work is not well known, so that no one can practice it who is not, so to speak, born to it, or who does not have much talent and good judgment. For this reason and also because it is closely related to sculpture, whose arms are the support of its life, it is very highly esteemed. In order to describe the whole art in every part, I say that the greatest labors of both mind and body are required for its operations in the beginning, middle, and end. It is indeed true that these labors are endured with pleasure because they are associated with a certain expectation of novelty, produced by the greatness of art and awaited with desire, particularly since the artificer sees that it is an art pleasing and delightful even to ignorant men. As a result, as if ensnared, he is often unable to leave the place of work. To conclude: The outcome of this art is dependent upon and subject to many operations which, if they are not all carried out with great care and diligence and well observed throughout, convert the whole into nothing, and the result becomes like its name [cast away]. Therefore, having considered this work many times, with its extraordinary obstacles and the bodily labors heavy as a stevedore's, instead of exalting it with praise, I wish to say that it is such that a man of noble birth, even though he be gifted or be drawn to it by pleasure, should not practice it and could not unless he is accustomed to the sweat and many discomforts which it brings. He must suffer the great natural heats of summer as well as those excessive and continuous ones from the enormous

Jan 1, 1942

H. M. BOYLSTON, Cambridge, Mass.-I would first like to ask what machine Capt. Bellis used to make his tests on impact strength. I have made some tests with the Charpy impact machine, the specimen being supported at both ends and nicked in the middle, and, find that the results do not always agree with those obtained by the Izod and other machines. I would also like to ask what effect the composition and heat treatment of the tool steel had on the drilling of his rifle barrels, as compared, with the heat treatment of the steel itself? I notice that the analysis of the composition of steel used shows sulphur 0.050 and phosphorus 0.065; I should like to ask how those high limits of sulphur and phosphorus came to be allowed? I have some data which lead me to feel pretty certain that those high limits make for very unsafe steel in rifle barrels. It has never been explained to the satisfaction of all of us, why the manganese is so high: 1.22 per cent. I believe several reasons have been stated; among them, that it is high in order to compensate for the high sulphur, and also to increase the elastic limit and improve other physical properties of steel. Lastly, I wish to ask whether Capt. Bellis has tried any different methods of heat-treating his steel rifle barrels? Apparently these were all heat-treated before machining; has he had any experience with heat-treatment after machining, especially after drilling? Those questions may seem somewhat outside of the range of this -paper, but they are important, and if Captain Bellis can give us any information, it will be very helpful. Dr. J. A. MATHEWS,* Syracuse, N. Y.-The same subject was discussed here last year, and the earlier papers by Dr. Carle Hayward seem to indicate that nothing was gained by the length of time of 'tempering. (It should be borne in mind that his results were based upon electrical and magnetic measurements and not upon tensile tests.) That idea has been accepted as gospel by steel workers, until late years, and particu-larly in connection with alloy steels, on which there is no question that the effect of time of tempering is very marked.

Jan 4, 1918

By Raymond Mancha

TO determine the optimum inside dimension of an airshaft, it is necessary to strike the proper balance between the cost of power for air friction and turbulence losses within the airshaft, on the one hand, and the cost of sinking the airshaft, on the other. An airshaft larger than necessary is extravagant because the increased amortization rate exceeds the reduction in power cost. Conversely, an airshaft smaller than is needed wastes more power than can be justified by the corresponding reduction in amortization rate. The airshaft power is a function of the air volume Q cu. ft. per min. and the air-pressure drop p in. water gauge across the airshaft. † The airshaft pressure drop is calculated by the formula: R X l X O X Q2 P= 5-2 X A3 wherein R is the air-friction coefficient for the portion of the airshaft 1 ft. deep, 0 ft. in perimeter and A sq. ft. in area, when passing an air volume of Q cu. ft. per minute. The airpower w kw. dissipated within the airshaft is computed by the formula: w= 0.746Q X P 6345 With a combined over-all unit efficiency of the fan and drive of E per cent, the air-shaft power requirements become W = 100w There are 8760 hours per year, so with energy at I cent per kilowatt-hour the annual cost per kilowatt for continuous operation is $87.60; therefore, with energy at C¢ per kw-hr. the annual airshaft power cost MI dollars per year becomes: M1 = 87.60W X C which, expressed by the component parts, becomes: M1 V 5.2X4' / XQ Z 0.746 X 100 X 87.60 X C V 60 X E ) The amortization rate a dollars per year per dollar invested includes both depreciation and interest on the investment. These in turn involve the expected useful life of the airshaft and available molletary interest rate. For the purpose of this discussion the cost of airshaft sinking is assumed to comprise a fixed move-in charge Y dollars, which covers the cost of transporting, erecting and removing the shaft-sinking equipment and is independent of the air-shaft size. Also, it is assumed that the cost of shaft lining, if any, is fixed at $X per cu. yd. of lining material and that excava-

Jan 1, 1947

By Raymond Mancha

TO determine the optimum inside dimension of an airshaft, it is necessary to strike the proper balance between the cost of power for air friction and turbulence losses within the airshaft, on the one hand, and the cost of sinking the airshaft, on the other. An airshaft larger than necessary is extravagant because the increased amortization rate exceeds the reduction in power cost. Conversely, an airshaft smaller than is needed wastes more power than can be justified by the corresponding reduction in amortization rate. The airshaft power is a function of the air volume Q cu. ft. per min. and the air-pressure drop p in. water gauge across the airshaft. † The airshaft pressure drop is calculated by the formula: R X l X O X Q2 P= 5-2 X A3 wherein R is the air-friction coefficient for the portion of the airshaft 1 ft. deep, 0 ft. in perimeter and A sq. ft. in area, when passing an air volume of Q cu. ft. per minute. The airpower w kw. dissipated within the airshaft is computed by the formula: w= 0.746Q X P 6345 With a combined over-all unit efficiency of the fan and drive of E per cent, the air-shaft power requirements become W = 100w There are 8760 hours per year, so with energy at I cent per kilowatt-hour the annual cost per kilowatt for continuous operation is $87.60; therefore, with energy at C¢ per kw-hr. the annual airshaft power cost MI dollars per year becomes: M1 = 87.60W X C which, expressed by the component parts, becomes: M1 V 5.2X4' / XQ Z 0.746 X 100 X 87.60 X C V 60 X E ) The amortization rate a dollars per year per dollar invested includes both depreciation and interest on the investment. These in turn involve the expected useful life of the airshaft and available molletary interest rate. For the purpose of this discussion the cost of airshaft sinking is assumed to comprise a fixed move-in charge Y dollars, which covers the cost of transporting, erecting and removing the shaft-sinking equipment and is independent of the air-shaft size. Also, it is assumed that the cost of shaft lining, if any, is fixed at $X per cu. yd. of lining material and that excava-

Jan 1, 1947

By T. H. Alden

In several recent studies of fatigue fracture in single-phase metals, tests have been made using the condition of essentially constant plastic strain amplitude.1-4 This procedure departs from the more common practice of holding the amplitude of stress constant. From these studies have emerged two important generalizations about the behavior of metals during cyclic straining. First, measurements of the stress amplitude, required to impose the fixed plastic strain amplitude, have shown that the rate of cyclic strain hardening in annealed metals is rapid in the early cycles but decays quickly to a very low value.1"5 This behavior is displayed particularly for a range of strain amplitudes below about 2 pct and at low and high temperature. Frequently, the hardening rate becomes so low that one can determine a "saturation" stress. This stress increases with strain amplitude. In addition, an experimental relation between fracture life and plastic strain amplitude was obtained by Coffin and Taternelli,' namely N 1/2 ep = constant. For several metal:;, this equation has been shown to hold down to a strain amplitude of 0.1 pct. Whether it also holds in the "low amplitude" range (lives of more than about 105 cycles) has not been established. The importance of the saturation stress level (a value derived from strain hardening measurements) to the question of fracture life (the usual quantity of interest of fatigue testing) lies in the observation that cracks start to form when the cyclic hardening rate is essentially zero, and not before.4"5 This point suggests immediately a means of relating tests at constant stress and constant strain amplitudes. When making comparison, the stress in a constant stress test is to be identified with the saturation stress in a constant strain test. If these ideas are correct, then it should be possible, using the relation between fracture life and strain amplitude and experimental curves of saturation stress versus strain amplitude, to predict the fracture life as a function of stress, i.e. predict the S -N curve, for low stress fatigue. Saturation stress amplitude-plastic strain amplitude data, obtained in tension-compression, exist only for a few metals and for relatively high amplitudes of strain. Comparable S -N curves (push-pull loading) were known by the author only for OFHC copper. Values for this metal taken from Ref. 2 are shown in Fig. 1. The strain amplitudes, the lowest

Jan 1, 1962

By G. P. Walters, W. C. Fuller

THE production of thin films of beryllium became essential early in the irradiation program at Harwell in order to study the fundamentals of irradiation damage in this metal. In common with other metals, electron-microacope specimens of beryllium can be produced by different techniques. The techniques used to produce thin-film specimens varied according to the starting material. Most of the starting material was -0.060 in. thick. Large-area specimens (1 in. long by 0.5 in. wide) were chemically thinned to -0.005 in. thick in a solution containing 85 pct orthophosphoric acid, 10 pct chromium trioxide, and 5 pct sulfuric acid at 70°C prior to electropolishing. Small-area specimens, Fig. 1, had to be mechanically thinned prior to electropolishing because chemical thinning considerably reduces the area as well as the thickness. Mechanical thinning tends to produce a worked layer about 0.002 in. deep and hence this method cannot be used to thin bulk specimens below about 0.005 in. thick. Mechanical thinning is carried out by mounting the specimen on perspex then carefully polishing on wet grinding papers. Polishing is continued until about half the initial thickness is removed; the reverse side is then polished in a similar manner. After the bulk specimens have been mechanically or chemically thinned to -0.005 in. they are elec-tropolished in the solution shown in able I at 50" to 80°C. This solution should be prepared by adding the chromium trioxide to the orthophosphoric acid and then the glycerol last. The glycerol should be added slowly because a vigorous effervescence can occur. Electropolishing is carried out by holding the specimen in stainless-steel tweezers and gently agitating in the solution. Masking or "window" techniques are not required for beryllium, good microscope specimens being obtained from the edges of elec-tropolished foils. A stainless-steel beaker should be used, acting as the cathode and solution container. A closed circuit voltage of 30 v is used for polishing. Too low a voltage produces a matt surface and pitting occurs when it is too high. The solution temperature is important. If it is too low, the solution is viscous and bad polishing results and, if too high, etching of the specimen occurs. After electropolishing, the foils are thoroughly

Jan 1, 1963

By B. E. Lindsly

The withdrawal of gas and/or oil in appreciable quantity from a natural oil reservoir causes the pressure within the reservoir to diminish, and if the oil is completely saturated with gas, this dissolved gas begins to evolve from solution. The liberation of gas from solution in oil causes the oil to change in several ways, the principal changes being: (1) reduction in volume or "shrinkage"; (2) increase in specific gravity (decrease in degrees A.P.I.); (3) decrease of energy in the oil; (4) increased viscosity; (5) increased surface tension. As the writer's investigations have been concerned more with the first three items than with changes in viscosity and surface tension the following discussion relates particularly to the volumetric shrinkage of the oil, to the increased specific gravity, and to the decreased energy in the oil, each caused by the liberalion of dissolved gas. One of the most surprising facts that have developed in the study of high-pressure well-head and "bottom-hole" samples is the great reduction in volume that occurs in some oils when the naturally dissolved gas is liberated. High-pressure samples taken from well heads in the Oklahoma City, Kettleman Hills and Ventura, Calif., fields decreased in volume from 11.2 to 40.5 per cent when the dissolved gas was liberated in reducing the pressure on the sample to atmospheric. The amount of shrinkage an oil undergoes when gas is liberated depends upon the quantity of gas liberated and also upon its composition. A given volume of the heavier gases, propane and butane for example, will occupy more space in the oil than an equal volume of methane. The reason for this probably is that the molecules of the heavier gases are larger than those of the lighter gases. When gases are not in solution, and particularly when they are at low pressures, the distance between the gas molecules is so much greater than the dimensions of the molecules themselves that the mere size of the molecules has little effect upon the space occupied by the gas, Avogadro's hypothesis, which in effect states that all gases under the same conditions have the same number of molecules per unit volume, relates to this phenomenon. The fact that the heavier gases occupy more space than the lighter gases in the oil, and

Jan 1, 1934

By William Hutton Blauvelt

The type of gas producer in which the ashes are fluxed and run off as slag was among the very earliest made. Ebelmen built the first one in 1840 at Audincourt, France, only a year after the installation of the first gas producer of which we have record. Charcoal was used as the fuel, with blast-furnace slag and clay as flux. My interest in this type of producer began when as a boy I saw the fluxing producer at Chester, N. J., which was invented by W. J. Taylor, and described by him in 1881.' This producer was invented independently by Mr. Taylor to meet the difficulties he experienced in making producer gas for roasting sulphurous iron ores. It will be of interest to review briefly his description of his producer. It was built like a small blast furnace, having a hearth 24 in. in diameter and 24 in. high. The bosh angle was 25' from the vertical; the diameter at the bosh 4 ft. and at the top 3 ft.; the total height 12 ft. The producer contained one water-cooled tuyere 12 in. above the bottom, with a 1.5-in. nozzle. Depth of the coal above the tuyere, 6 ft. Mr. Taylor mixed the coal with from 30 to 40 per cent. of basic blast-furnace slag to flux the ash. Occasionally some limestone was also used, but never limestone alone, as the use of the furnace cinder gave a larger volume of slag and made it easier to maintain a proper fluidity. The producer was blown with a small Weimer blowing engine, delivering 300 ft. of air per minute, at from 1 to 1.5 lb. pressure. The slag was tapped every 2 hr. and was black and glassy in appearance. Broken or egg size anthracite was used. The fine sizes of anthracite could not be made to work. Mr. Taylor expressed the belief that bituminous coal could be used if not too fine, but no experiments were made with this coal. Runs were made of four weeks' duration, with no stops or changes. Mr. Taylor reported the following advantages: 1. Excellent gas, very uniform in quality. The high fuel bed permitted no air to pass unconsumed, and the gas was almost entirely free from carbonic acid.

Jan 1, 1914

By Paul Gordon, A. S. Iyer

Apreliminary investigation has been carried out on the annealing behavior of explosively deformed copper as compared to that of conventionally deformed copper, using hardness, stored energy, and the sharpening of X-ray spots on Debye rings as the measures of annealing. Some metallographic observations were also made. Two purities of copper were studied. The first was tough pitch copper obtained as a small piece from the guard ring of a sample explosively deformed to approximately 500 kbars.* The second consisted of mentedand deformed these samples quite badly so that only a few small fragments were available for the annealing experiments. As a result, little in the way of quantitatively significant data was gleaned from the measurements. However, several important qualitative differences between the annealing of explosively deformed and conventionally deformed copper have been observed. It is these effects which are described in this report. Fig. 1 presents the results of hardness and stored energy measurements during the annealing of the high-purity copper after explosive and after conventional deformation. The data for the conventionally deformed copper were taken from the work of Gordon;' in this copper it is evident that most of the stored energy is released concommittantly with the hardness drop. As shown in orddon's' investigation, these effect:: are definitely associated with recrystal-lization. In the case of the explosively deformed copper, on the other hand, a large fraction of the stored energy is released before any appreciable hardness change takes place. At 160°C about 40 pct, and at 170°C about. 80 pct, of the stored energy appears to have been released prior to the onset of softening, i.e., undoubtedly prior to recrystallization. In view of the facts that the hardness and energy measurements were made on separate samples and that there is reason to suspect that the intensity of the explosive deformation from sample to sample may not have been uniform, a check run was carried out in which both energq release and hardness changes were measured cnn the same sample. The results of this run, shown in Fig. 2, confirm the conclusion that much of the stored energy is released before the hardness begins to change appreciably. In an effort to obtain some idea of the activation energy associated with the early release of energy, a single callorimetric sample was annealed in two steps, first at 149.5"C and then at 159.5"C, Fig. 3.

Jan 1, 1962