Search Documents

By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By S. A. Ford

A SHORT and accurate method for the estimation of manganese in iron and steel is of great advantage to Bessemer works, and I think it may be of interest to some of the members of the Institute to give in detail the process in use in the laboratory of the Edgar Thomson steel works. The process is based on the reaction first described by Beilstein and Jawein.* The steel, spiegel, or iron is dissolved in strong nitric acid, sp. gr. 1.½. Evaporation to dryness is not necessary, unless the amount of silicon is large, as in the case of certain pig irons. Then, as a clogging of the filter in the subsequent filtration is apt to follow, dissolve first in a dish in hydochloric acid, quickly evaporate to dryness, redissolve in the strong nitric acid, boil, and while boiling throw in crystals of chlorate of potash from time to time. Violent action ensues, yellow fumes are given off, and binoxide of manganese is precipitated, since it is insoluble in strong

Jan 1, 1881

By Richard Maclin Stewart

A priest at Shenandoah, Pa., one day persuaded the president of the Philadelphia & Reading Coal & Iron Co. to slush breaker waste and culm into old mine workings in order to save his church from being destroyed by surface subsidence. The year was 1864, the project was successful, and history recorded the first use of hydraulic backfilling. Shortly afterward, the method was applied to several eastern coal mines for area fill to control subsidence. In 1884, hydraulic backfilling was used to control a mine fire in the Schuylkill region of Pennsylvania. The idea was taken to Europe by German engineers and developed successfully at the Myslovitz colliery in Upper Silesia in 1901. From there it was applied to several mines throughout Europe.

Jan 4, 1958

By John Henry Harden

IN 1874, with Mr. H. Y. Attrill, of Baltimore, Md., I made an examination of some property at Goderich with reference to sinking for and mining salt. With this end in view we visited all the wells in the neighborhood, but the information sought being of so unreliable a character I advised the putting down of a borehole on the property. This has since been done, the result of which has lately been published by Dr. T. Sterry Hunt in the Toronto Globe. From this there appears to have been passed through six beds of salt of an aggregate thickness of 123 feet. Rock-salt was known to exist, for, by the boring of existing wells, small crystals had been brought to the surface in the dirt, but no attempt had before been made to obtain a reliable sample or to prove the number and thickness of the beds. The question now remaining for discussion is, shall the present method of obtaining the salt be continued, or shall the beds be won by a shaft in a regular mining fashion, by which means the salt may be gotten in a condition almost ready for the market? The present mode of obtaining salt is by boreholes from 6 inches to 8 inches in diameter drilled to the beds, into which is inserted a pump. The "feeders" of fresh water intersected in drilling the well are allowed to descend on the outside of the pump-tube to the salt beds and there become saturated, when, on use of the pump, brine is obtained for evaporation. In the beginning brine can only be had in limited quantity, but by the daily application of the pump, and the gradual solution of the salt, a larger surface becomes exposed to the action of the fresh water, and a continuous supply of brine is obtained. It will then be understood that the supply of brine is dependent upon the feeders of fresh water intersected in boring the well, which, we are told, have never shown any sign of diminution, and this is the water that must be encountered in sinking a shaft. There are ten wells in operation at Goderich, the most important one to the present project being known as the Hawley Well, located at an elevation a few feet above Lake Huron at the mouth of the river Maitland, at a much lower level and nearer to the proposed shaft than any other well in the district. At this well the feeders

Jan 1, 1877

By John Henry Harden

IN 1874, with Mr. H. Y. Attrill, of Baltimore, Md., I made an examination of some property at Goderich with reference to sinking for and mining salt. With this end in view we visited all the wells in the neighborhood, but the information sought being of so unreliable a character I advised the putting down of a borehole on the property. This has since been done, the result of which has lately been published by Dr. T. Sterry Hunt in the Toronto Globe. From this there appears to have been passed through six beds of salt of an aggregate thickness of 125 feet. Rock-salt was known to exist, for, by the boring of existing wells, small crystals had been brought to the surface in the dirt, but no attempt had before been made to obtain a reliable sample or to prove the number and thickness of the beds. The question now remaining for discussion is, shall the present method of obtaining the salt be continued, or shall the beds be won by a shaft in a regular mining fashion, by which means the salt may be gotten in a condition almost ready for the market? The present mode of obtaining salt is by boreholes from 6 inches to 8 inches in diameter drilled to the beds, into which is inserted a pump. The "feeders" of fresh water intersected in drilling the well are allowed to descend on the outside of the pump-tube to the salt beds and there become saturated, when, on use of the pump, brine is obtained for evaporation. In the beginning brine can only be had in limited quantity, but by the daily application of the pump, and the gradual solution of the salt, a larger surface becomes exposed to the action of the fresh water, and a continuons supply of brine is obtained. It will then be understood that the supply of brine is dependent upon the feeders of fresh water intersected in boring the well, which, we are told, have never shown any sign of diminution, and this is the water that must be encountered in sinking a shaft. There are ten wells in operation at Goderich, the most important one to the present project being known as the Hawley Well, located at an elevation a few feet above Lake Huron at the mouth of the river Maitland, at, a much lower level and nearer to the proposed shaft than any other well in the district. At this well the feeders

By C. R. Kuzell

The Editor desires to call attention to the charts in the paper of the above title which were published in the August Bulletin on pages 2190 and 2191. It was impracticable to include in the Bulletin. charts of sufficient size to be used as working diagrams for the direct determination of operating values, but the Institute is prepared to furnish copies of these charts on a large-size scale, at a moderate cost, to those who desire to have them for this purpose. CORRECTIONS Page 2185, line 3. For "is accessory apparatus" read "in accessory. apparatus." Page 2188. Substitute for lines 11 and 12: Nitrogen, oxygen, carbon monoxide, Cp = 6.50 + 0.0010T Hydrogen, Cp = 6.50 + 0.0009T

Jan 9, 1914

By J. W. Lewis

This review covers that portion of the area between the Llano mountains and the Red River which lies between Fort Worth and Abilene. The counties and fields included are listed in Tables 1 and 2. During 1929 there was a marked lull in both prospecting and development in this part of Texas. Archer, Coleman, Cooke, Wilbarger and Young were the counties most active. The total gross production of the year was 52,611,000 bbl., 3 per cent. more than for 1928. The production of the Coleman, Cooke-

Jan 1, 1930

Discussion of the paper of Frederic P. Dewey, presented at the Cleveland Meeting, October, 1912, and printed in Bulletin -No. 70, October, 1912, pp. 1075 to 1101. EDWARD KELLER, Perth Amboy, N. J. (communication to the Secretary *) :-Mr. Dewey, in his paper, offers a liberal addition of new data to those already to be found in the technical literature on this subject. However, now as before, the work issuing from the U. S. mints and assay-offices conveys the impression that systematic sampling in those institutions is more or less a secondary consideration, the chief attention being given to the principle of producing approximately homogeneous bars; recourse being taken to remelting or refining the bullion. This practice has been definitely rejected in the realm of copper-bullion sampling, for the reason that in such operations there are always unaccounted losses. Does not the same objection hold true for gold-bullions; although, perhaps,in a lesser degree ? Differences of opinion would seem justified on the following statements made by Mr. Dewey: 1. "Only two classes of alloys can form homogeneous bars-those that are solid solutions, and the eutectics."

Jan 3, 1913

By D. E. Munson, H. J. Sutherland

Surface subsidence caused by underground mining is described through complementary influence functions. The complementary functions developed here differ from the simple functions previously used in that the surface displacement is the result of the combined contributions of the mined and unmined zones. This eliminates computational difficulties experienced with the simple functions in determining the deflections above the rib side and in the eventual application of influence functions to complex room-and-pillar configurations. Although the analysis framework presented is intended for predicting subsidence over complex mine configurations, use of the complementary functions is illustrated adequately by application to a longwall panel of the Old Ben No. 24 coal mine.

Jan 1, 1982

By J. E. Johnson

Discussion of the paper of Mark A. Amnion, presented at the Cleveland meeting October, 1913, and printed in Bulletin No. 70, October, 1913, pp. 1167 to 1 79. J. E. JOHNSON, JR., Ashland, Wis.:-Mr. Amnion's paper is of great value and it is not with any desire to reflect. on it that I wish to make some comments on the use of the scleroscope. We obtained one on trial some months ago and made very extensive tests with it, but without getting very satisfactory results. The readings on good car-wheels and bad ones were just about the same, but the factor in its use most likely to produce erroneous results is a variation in the thickness of the specimen being tested. In order to find out something on this subject we cut a thin disk, about -1,: in. thick, off a brass rod; then one 0.25 in. thick, and another about 1 in. thick, put the surfaces of all in about the same condition and tested them with the scleroscope. The readings varied widely; the resilience of the anvil evidently entered to a very high degree on thin pieces. By putting a soft cushion between such a thin specimen and the anvil, and forcing it up against the tube, the softness of the cushion cut off the resilience of the anvil and the results were more like those of the thick specimens. After a thickness of 1 in. was passed, the specimen seemed to have mass enough so that the resilience of the anvil no longer played an important part, and above that thickness results on different materials would be comparable, even though the thicknesses differed. But in order to get comparable results on thin specimens the thickness of those being tested should be the same. I should like to ask how the variations introduced in this way were overcome, so as to get strictly comparable results. Mr. AMMON :-.I have not had much experience in that, but the scleroscope is simply an indication of the surface harden-

Dec 1, 1912

By M. E. Herrera

The use and effectiveness of sealants in under-ground mines is a recognized and well accepted practice by many people in the mining industry. Their use however in many cases is to correct, or attempt to correct, problems that might have been avoided with sealant use in the early stages of development, and continued thereafter.

Jan 1, 1982

By Arthur C. Simmons

The area producing Pennsylvania-grade crude oil declined sharply in 1943, with a daily average production in the entire area of 71,056 bbl. as against a daily average in 1942 of 77,786. The total decline in the Pennsylvania-grade area amounted to 2,456,311 bbl., and 1,g81,z71 bbl. of this occurrcd within the state of Pennsylvania. The principal decline occurred in the Bradford field, where it was caused primarily by a drastic reduction in well completions. All of the zones in the Pennsylvania-grade producing area showed a decline except the part of Ohio that produces that grade, where production increased very slightly over 1942. Table I shows the average daily production by months for the several districts of the area. Table z is a comparison of the production in the two districts within the state of Pennsylvania. It is interesting to note that the Bradford field produced approximately half the total quantity of Pennsylvania grade but accounted for nearly three-fourths of the decline in production from the previous year. It is believed that this decline is ocasioned by restrictive price ceilings and a lack of adequate manpower to drill the necessary wells to maintain production. Stocks of Pennsylvania Grade At the beginning of 1942, stocks of Pennsylvania-grade crude totaled 3,196,000 bbl. and at the beginning of 1943 they totaled 2,626,000 bbl. At the end of 1943 the stocks of Pennsylvania-grade crude had declined to 1,95z,000 bbl. The available crude stocks have been almost completely consumed, as nearly all of the present crude stocks are "unavailable" and required for

Jan 1, 1944

By Arthur C. Simmons

The area producing Pennsylvania-grade crude oil declined sharply in 1943, with a daily average production in the entire area of 71,056 bbl. as against a daily average in 1942 of 77,786. The total decline in the Pennsylvania-grade area amounted to 2,456,311 bbl., and 1,g81,z71 bbl. of this occurrcd within the state of Pennsylvania. The principal decline occurred in the Bradford field, where it was caused primarily by a drastic reduction in well completions. All of the zones in the Pennsylvania-grade producing area showed a decline except the part of Ohio that produces that grade, where production increased very slightly over 1942. Table I shows the average daily production by months for the several districts of the area. Table z is a comparison of the production in the two districts within the state of Pennsylvania. It is interesting to note that the Bradford field produced approximately half the total quantity of Pennsylvania grade but accounted for nearly three-fourths of the decline in production from the previous year. It is believed that this decline is ocasioned by restrictive price ceilings and a lack of adequate manpower to drill the necessary wells to maintain production. Stocks of Pennsylvania Grade At the beginning of 1942, stocks of Pennsylvania-grade crude totaled 3,196,000 bbl. and at the beginning of 1943 they totaled 2,626,000 bbl. At the end of 1943 the stocks of Pennsylvania-grade crude had declined to 1,95z,000 bbl. The available crude stocks have been almost completely consumed, as nearly all of the present crude stocks are "unavailable" and required for

Jan 1, 1944

New Products Equipment

Jan 6, 1950

By J. B. Darby, P. A. Beck

IN a previous publication,' the 1200°C isothermal section of the Cr-Mo-CO system was surveyed. It was found that starting from the binary (Cr,Co)a, the u phase extends deep into the ternary system in the form of a narrow band, which, when extrapo-

Jan 1, 1956

[ ]

Jan 1, 1907

By R. V. Riley

IN the metallographic examination of the alloys of iron and silicon, several investigators1-' have reported on the occurrence of an unusual type of etched structure, particularly in the alloys of higher silicon content. This, the so-called "barley shell" structure, has been observed with iron-silicon alloys over a wide range of silicon content, and under certain circumstances it can be seen upon the micro-sections of pure iron. The barley shell structure may be demonstrated most easily with iron-silicon alloys in the range 8 to 20 pct Si after etching in a hydrofluoric acid base etchant. Two etchants which produce the structure are: Corson's reagent, which is 2 parts hydrofluoric acid, 1 part nitric acid, and 2 parts glycerol; and picric acid reagent, which is 1 part hydrofluoric acid and 1 part saturated solution of picric acid in alcohol. Both when freshly prepared and used for etching commercial silicon-iron alloys containing 14 to 16 pct Si, invariably produce the barley shell structure shown in Fig. la. It is now well known that the barley shell structure is a pseudomorph and the true structure of an alloy of this composition consists of a single phase of silico-ferrite together with graphite as shown in Fig. lb. Lower silicon alloys and even pure electrolytic iron may also be etched in the above reagents to give the barley shell provided the etchant has been either: 1—Stored in contact with glass or silica, or 2—used previously for etching an iron containing silicon. Pure iron etched in perfectly pure hydrofluoric acid base etchants free from silicon contamination gives a normal structure free from the barley shells. Therefore, although the hydrofluoric acid in the reagent primarily is responsible for the barley shells, silicon, or its compounds, also must be present, either in the etching reagent or in the specimen. It was of considerable interest to the author to read the paper by Wachtell,? in which the barley shell etch was deliberately used for the identification of the boundaries of high and low silicon areas in diffusion experiments made upon laminate bars of compacted and sintered pure iron and ferrosili-con powders. This method of utilizing the barley shell etch is novel and in the hands of the investigator gave a useful differentiation between the high and low silicon areas in those specimens. For the reasons already given, however, the technique is not to be regarded as of universal application. Misleading results might be obtained, for example, if two or more specimens were etched in the same etchant. Fresh pure reagents only must be used each time. Provided this is done and the investigators are well aware of the limitations of the method, then the barley shell pseudomorph can be made of limited use in distinguishing between higher and lower silicon areas in a microspecimen of a ferrous material. The greatest of care must be exercised in the interpretation of the results which may be regarded as qualitative only and may, in fact, not be specific to silicon alloys.

Jan 1, 1952

SAMUEL T. HOYT,? Minneapolis, Minn. (written discussion||).-The subject of grain inheritance in iron and steel is apparently one which can he considered from the point of view of the two laws governing the rate of formation of crystal nuclei and the linear velocity of crystallization, which have been investigated by Tammann and collaborators, and of the additional law of coalescence. According to the work of Tammann, both the nuclei number, which is taken to be the number of crystal nuclei to form per unit volume per unit time, and the linear velocity of crystalli-

Jan 5, 1918

By G. K. Burgess

J. W. RICHARDS, South Bethlehem, Pa.-I think my affections are still rather with the radiation pyrometer than the optical pyrometer, for practical use, and I wish that Prof. Burgess would use the two together, under the same conditions, using the optical as his standard, if he prefers. Then, assuming the optical emissivity which he feels is correct for the optical pyrometer, he could calculate the thermal emissivity for use with .the radiation pyrometer. If we could thus get reliable values for the thermal emissivity, we could then use the radiation pyrometer, and would avoid the use of the standard lamp, which has to be frequently calibrated for use in the optical pyrometer. It is very advisable to distinguish carefully between the terms optical emissivity and thermal emissivity. There -is considerable confusion caused by the bare statement that molten iron has an emissivity of so much, meaning by that its optical emissivity, for a light wave of a certain length; whereas what we want in the radiation pyrometer is its total ther-

Jan 4, 1917

Jan 1, 1910