Search Documents

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

IN speaking, on the subject, "Engineer-Citizens," at the Lehigh Valley Mineral Industries Conference dinner, on April 26, at Easton, Pa., George Otis Smith, Director of the United States Geological Survey and President of the American Institute of Mining and Metallurgical Engineers, said in part: "It would be carrying coke to Connellsville to bring to the Lehigh Valley the idea that mineral resources are the foundation of national prosperity. Unfortu-nately, however, this obvious, fact is not everywhere recognized. Too many of our economists, journalists, statesmen and other dopesters of present business con-ditions stress the human factor so strongly that they overlook the material with which men work out their destiny. To them the financial psychology of Wall Street and the political logic of Capitol Hill and the business commonplaces of Main Street all loom far larger than the geology of the Lehigh Valley or the engineering triumphs of Bethlehem, or, the creative thinking at Lehigh and Lafayette. "The present situation in the industrial and .business world is a complex of interacting causes and reacting effects not easily itemized and entered on our trial balance sheet. But, chief among the liabilities of today is the excess of production capacity in most branches of industry. The farmer has no. monopoly in his desire for relief. Whether your professional connections are with steel or cement, coal or oil, copper, or zinc, you; know too well that for, the moment America is over-engined, and you keenly realize the ever-present hazard of industry speeding up regardless of the curves or grades just around the corner.

Jan 5, 1928

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' 26' 38'' north, and long. 119' 55' 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 Robert W. Hunt

THE memorable features of American history have been making fast during the last century, and notably so since 1860; and they are by no means confined to political or to any one branch of scientific development. Of all the industrial arts, none show a greater change or a mightier progress than the Bessemer manufacture. And this year, while we are celebrating the first centennial of our national life, we can also celebrate the first decennial of American Bessemer practice. While not forgetting or undervaluing what has been done in other countries, I have thought that a brief history of the introduction and development of the Pneumatic or Bessemer process in America would be of interest. In 1863 the Kelly Pneumatic Process Company was formed and an arrangement entered into with William Kelly, who had taken out letters-patent of the United States, Nos. 16,444 ; 17,628, re¬issued as 505; 18,910, dated January 10th, 1857 ; June 23d, 1857; November 3d, 1857; and December 22d, 1857, respectively. This association was composed of the Cambria Iron Company, E. B. Ward, Park Brothers & Co., Lyon, Shorb & Co., Z. S. Durfee, and, later, Chouteau, Harrison & Valle joined the combination. Not satisfied with possessing the control of the Kelly patent, they sent Mr. Z. S. Durfee to England, to secure for this country Mushet's patent on recarburization, No. 17,389, dated May 26th, 1857, the same having been taken out in England on September 22d, 1856. In this Mr. Durfee was successful. Previous to the application of William Kelly for a patent, Henry Bessemer, of England, had taken out patents dated February 12th, 1856, and August 25th, 1856, in this country. Kelly claimed priority in the discovery of the principles of the process, and the Patent-office allowed his claim by granting him his patents. In the autumn of 1862 Mr. Alexander L. Holley, while in England, was impressed with the importance of Mr. Bessemer's inven¬tion, and so fully foresaw its future, that, upon his return to the United States, he induced Messrs. John A. Griswold and John F. Winslow, of Troy, New York, to join him in endeavoring to possess Bessemer's American patents. Mr. Holley returned to England in

Jan 1, 1877

By H. P. Moore, R. W. Fenn, Harold Margolin, W. R. Hibbard

DEFORMATION lines, also called etch markings or strain markings, are noneffaceable lines developed in individual grains by etching a metal specimen which has been cold worked sufficiently to cause atomic non-conformity or slight orientation differences within the grains. Etching occurs more rapidly at these lines of high chemical reactivity to produce a result similar to that revealing grain boundaries.1 Wider etching effects forming bands have been found. They are believed to be bands of deformation lines which form areas of measurably different orientation from the crystal matrix. The crystallite rotations causing these bands have been shown by Barrette to contribute to deformation textures. Although deformation lines have been observed in many metals, the amount of deformation required for their appearance has been established only in general terms. Mathewson and Phillips3 observed the first appearance of deformation lines in cold-rolled alpha brass at about 20 pct reduction in thickness using the standard ammonium hydroxide hydrogen peroxide etchant. Price and Davidson4 noted deformation lines in common high brass after 26.5 pct reduction by cold rolling using the same etchant. Johnson' observed dark thick forklike lines in 99.99 pct pure copper reduced 31.8 pct. Adcock6 observed deformation lines in 80-20 copper-nickel alloy rolled 50 pct. Samans7 found no deformation lines in alpha brass single crystals cold rolled 9.5 pct but they did appear after 25 pct reduction using ammonium hydroxide and hydrogen peroxide etchant. Barrett and Levenson8 observed deformation bands in drawn polycrystalline iron at very small reductions in area and noted that their initial appearance perhaps depends on grain size and other conditions. They reported deformation bands in a single crystal of iron reduced 6 pct by drawing. Brick9 noted that deformation lines in 70-30 brass apparently associated with {111} planes appeared after reductions of from 20-50 pct by cold rolling. Brick and Williamson10 noted that in single crystals of 70-30 alpha brass "as in polycrystalline brass, no deformation markings appeared until reductions exceeded 20 pct." Cook and Richards11 reported that in copper cold rolled less than about 50 pct few strain markings were apparent but for higher. reductions many strain markings appeared transverse to the rolled direction. In a review article Brick and Phillips12 noted that previous studies had not shown deformation lines in cold rolled alpha brass

Jan 1, 1948

By R. P. Rothwell

IN January last I published in the Engineering and Mining Journal a table giving, with a considerable degree of accuracy, the production of anthracite coal for the year 1874. At that time it was impossible to give any correct estimate of the production of bituminous coal, for the returns I had been able to secure from such distant and scattered districts were not always forwarded punctually, and the work of -obtaining anything like a true estimate of the coal mined in districts from which I was unable to obtain official returns was both laborious and tedious. As will be seen from the detailed reports furnished herewith, I have succeeded in obtaining tolerably accurate returns of 20,093,704 tons; and upon careful revision by numerous well-informed local authorities, my first estimate of the amount of coal not officially returned to me has grown very considerably; indeed, as I get more information on the subject I find that our bituminous coal production greatly exceeds the amount we have been accustomed to hear it placed at, aggregating as it does, 26,465,704 tons. Mr. Andrew Roy, State Inspector of Mines for Ohio, has reported the production of Ohio at 4,168,445 tons, while his first estimates were but 3,820,000 tons; and similarly, in other cases, the more full the returns direct from the mines the more incorrect do I find all previous reports. I am able now to furnish, not an accurate statement, indeed, but by far the most full and reliable one that has yet been published of our coal production. The amount of labor involved in obtaining this admittedly imperfect report has been simply enormous. In the following tabular statement it will be perceived that Pennsylvania produces nearly one-half of all the bituminous coal mined * Since this paper was read fuller reports from some of the States whose production had been "estimated" have modified the figures given. The most serious error is in California, which produces probably 200,000 tons less than these figures. Oregon and Washington territories also yield smaller amounts than here reported; but these reductions are probably fully compensated by fuller reports from other States that were here underestimated. The correct aggregate amount will not vary much from that here given. Early in 1876 I will be able to give a fuller and more accurate report for the year 1875.

Jan 1, 1875

By J. E. Brantly

In October 1939, a drilling program was commenced on the Atlantic seaboard of Brazil, with three steam rotary rigs of medium capacity. One of these was assigned to the State of Alagbas and the other two to the State of Bahia. During the remaining few months of 1939 and during the year 1940, some eight wells were drilled, two in Alagbas and six in Bahia. Two small producers were found in the latter state. In early 1941 three medium-weight Diesel rigs were added to the equipment, thus permitting the drilling of some 15 wells during the year 1941. The two small producers found in 1940 in the State of Rahia were near the city of Silo Salvador. In 1941 three additional small wells were brought in, in the same area, and a further producer on an isolated structure some 75 km. to the northwest of this production. No commercial production has been found in the State of Alagbas. Approximately 26 wells have been drilled or are drilling, six of which are producers— five in one area and one in another. The program for 1942 calls for the development of the two areas in which wells have been found and also the drilling of several wildcat structures located either by geophysics or surface geology. All production in the area of the several producing wells is somewhat less than 2000 ft. and in the other area about 3800 ft. The area of the several wells is known as the Lobato field, and is practically within the city limits of Sao Salvador. The area 75 km. northwest of the city will be known as the Candeias field.

Jan 1, 1942

By J. E. Brantly

In October 1939, a drilling program was commenced on the Atlantic seaboard of Brazil, with three steam rotary rigs of medium capacity. One of these was assigned to the State of Alagbas and the other two to the State of Bahia. During the remaining few months of 1939 and during the year 1940, some eight wells were drilled, two in Alagbas and six in Bahia. Two small producers were found in the latter state. In early 1941 three medium-weight Diesel rigs were added to the equipment, thus permitting the drilling of some 15 wells during the year 1941. The two small producers found in 1940 in the State of Rahia were near the city of Silo Salvador. In 1941 three additional small wells were brought in, in the same area, and a further producer on an isolated structure some 75 km. to the northwest of this production. No commercial production has been found in the State of Alagbas. Approximately 26 wells have been drilled or are drilling, six of which are producers— five in one area and one in another. The program for 1942 calls for the development of the two areas in which wells have been found and also the drilling of several wildcat structures located either by geophysics or surface geology. All production in the area of the several producing wells is somewhat less than 2000 ft. and in the other area about 3800 ft. The area of the several wells is known as the Lobato field, and is practically within the city limits of Sao Salvador. The area 75 km. northwest of the city will be known as the Candeias field.

Jan 1, 1942

By H. H. Alexander

IN the early part of the last century textile fabric was used for the filtration of products of combustion and lampblack was obtained by passing smoke through a series of canvas bags. Natural draft was, used to draw and force the smoke through the bags. About 1850 bag filtration was used for collecting zinc oxide. Around 1876 it was introduced for collecting the fume from lead-ore hearth smelting in. Missouri. Shortly afterward it was used, first at Portland, Me., and later at Canon City, Colo., for the collection and production of zinc-lead pigment in treating mixed zinc-lead sulphides. In 1890 the Globe Smelting & Refining Co., at Denver, Colo., installed a bag house containing 1,458 bags for the recovery of fume from silver-lead blast furnaces. This installation was too small to handle all of the gases and was increased to approximately 2,300 bags. . In 1900 the number of bags was again increased, making a total of approximately 2,800: The usual difficulties incident to new installations were encountered, but they were gradually overcome and the bag house became accepted as standard practice for this class of smelting. As all of the bag houses built since have followed the general lines of the Globe installation, a short description may be of interest. The general construction of the Globe bag house is shown in Figs. 1, 2, and 3. The building is 149 ft. 8 in. long by 67 ft. 4 in. wide and 40 ft. 2 in. high from the basement floor to the eaves of the roof, having brick walls 26 in. thick from the foundation up to the thimble floor, from there an 18-in. wall for 16 ft. and a 13-in. wall from this point to the top, a distance of 14 ft. 2 in. Additional stiffening is given to the walls above the basement by pilasters located every 16 ft. The end-wall construction is similar to that of the side walls with the exception of the spacing of the pilasters, which is somewhat greater. The roof is made of corrugated iron laid on 1-in. boards and supported by a timber frame work spaced 16 ft. apart resting on the basement partition walls. On top is a louver running the

Jan 8, 1914

By H. H. Alexander

In the early part of the last century textile fabric was used for the filtration of products of combustion and lampblack was obtained by passing smoke through a series of canvas bags. Natural draft was used to draw and force the smoke through the bags. About 1850 bag filtration was used for collecting zinc oxide. Around 1876 it was introduced for collecting the fume from lead-ore hearth smelting in Missouri. Shortly afterward it was used, first at Portland, Me., and later at Canon City, Colo., for the collection and production of zinc-lead pigment in treating mixed zinc-lead sulphides. In 1890 the Globe Smelting & Refining Co., at Denver, Colo., installed a bag house containing 1,458 bags for the recovery of fume from silver-lead blast furnaces. This installation was too small to handle all of the gases and was increased to approximately 2,300 bags. In 1900 the number of bags was again increased, making a total of approximately 2,800. The usual difficulties incident to new installations were encountered, but they were gradually overcome and the bag house became accepted as standard practice for this class of smelting, As all of the bag houses built since have followed the general lines of the Globe installation, a short description may be of interest. The general construction of the Globe bag house is shown in Figs. 1, 2, and 3. The building is 149 ft. 8 in. long by 67 ft. 4 in. wide and 40 ft. 2 in. high from the basement floor to the eaves of the roof, having brick walls 26 in. thick from the foundation up to the thimble floor, from there an 18-in. wall for 16 ft. and a 13-in. wall from this point to the top, a distance of 14 ft. 2 in. Additional stiffening is given to the walls above the basement by pilasters located every 16 ft. The end-wall construction is similar to that of the side walls with the exception of the spacing of the pilasters, which is somewhat greater. The roof is made of corrugated iron laid on 1-in. boards and supported by a timber frame work spaced 16 ft. apart resting on the basement partition walls. On top is a louver running the

Jan 1, 1915

By R. B. Sosman, J. C. Hostetter

It is well known that ferric oxide, Fe2O3, is paramagnetic, while magnetite, Fe3o4, is classed among the highly ferromagnetic substances. But magnetic data on oxides intermediate in composition between Fe2o3 and Fe3O4 have been almost completely lacking. Fe2O3 and Fe3O4 form a solid-solution series, according to present evidence.' In this series the properties change continuously from Fe2O3 toward Fe3O4, as the percentage of FeO increases from zero toward 31.03, which is the percentage in magnetite. It is possible that there is a break in the series near Fe3O4, but it has not yet been possible to establish the existence of such a break experimentally. The occurrence of solid solution in this series is shown by the dissociation pressure, or oxygen pressure in equilibrium with the oxides, which falls continuously over the range from Fe2O3 to Fe3O4. The oxygen-pressure curves at 1100" and 1200" are shown in Fig. 1. The existence of solid solution is also demonstrated by the continuous change in optical properties from Fe2O3 over to a composition containing about 18 per cent. FeO, at which point the opacity of the oxide becomes so great that it is impossible to obtain measurements at higher percentages of ferrous iron. Natural oxides of iron intermediate in composition between Fe2O3 and Fe3O4 are much more common than is generally supposed. If a mineral oxide is not strongly attracted by a small hand magnet and if it gives a red streak, it is usually labeled "hematite." If it is strongly attracted by the hand magnet it is usually labeled "magnetite" without further tests. As we shall show later, oxides containing from 1 up to 31 per cent. FeO can be thus erroneously lumped together as "magnetite." It is a fact, nevertheless, that the great bulk of natural oxides of iron lie fairly near either Fe2O3 or Fe3O4 in composition. The reason will be

Jan 1, 1918

By A. L. Mular

Two equations express the integral rate at which fines are produced from a homogeneous material: It has been demonstrated that the Gaudin-Meloy distribution for single fracture is equally applicable to multiple fracture and is related to the Gaudin-Schuhmann distribution at least when the distribution modulus a is close to unity. A, xoY was found to be independent of starting mass over the range studied when particle size was held constant. The equations are related to the input energy to the mill. In an earlier paper,' it was shown that when Mo g of uniformly sized homogeneous material is ground dry in a batch rod mill, the energy-size reduction equation is expressed at any time by the mass of unbroken starting material left at time t, ku is the size modulus of the portion Mo - Mt, and P is a constant that is generally equal to the distribution modulus a. If the power to the mill is constant, Et is proportional to time and Eq. 1 is rewritten where (Mo -Mt)/t is actually the integral rate at which fines are produced from a parent material, and A, is another constant. The size modulus, k,, is determined from the Gaudin-Schuhmann equation:2 where y is the cumulative fraction finer than any size x. Recently, Gaudin and Meloy derived a distribution equation for single fracture on the assumption that the random fracture of a homogeneous material produces daughter particles of similar shape. Their equation is given by where y is the cumulative fraction finer than size X, x, is the size of the unfractured parent, and r is designated the size ratio. Although Eq. 4 is derived for a single event, it should also approximately hold for a series of com-

Jan 1, 1962

By Truman H. Aldrich

The red, or fossiliferous, ore is found in the Clinton group of the Silurian formation. This group is from 100 to 500 ft. thick in Alabama, and its outcrops have been mapped by the State or the U. S. Geological Survey. In some places, it is entirely missing (doubtless islands in the Silurian Sea). In Etowah County, in part of Greasy Cove and vicinity, the upper seam is a coral reef impregnated with the red ore; in this same county, step faults bring up the ore in three or four practically parallel ridges. In Blount County and on Raccoon Mountain, the ore runs under the carboniferous rocks and outcrops in the valleys. When examining the logs of holes drilled for oil, wherever the drill has gone deep enough, the writer has found the Clinton group underlying the Warrior coal field. The following records of holes drilled primarily for oil, given in Bull. No. 22, Geological Survey of Alabama, show the presence of either ore or red rock, and suggest vast resources yet to be outlined and developed for ore in the future. The locations are given by number on the map. Hole No. 1 was drilled 6 miles southeast of Russellville, Franklin County, by the Woodward Oil & Gas Co. It passed through 160 ft. of the Clinton, but only a small show of red ore was found at 1280-1400 ft. A test well, No. 2, drilled near Atwood, Franklin County, in sectioil 26, township 8, range 14, penetrated the Clinton at 1608 ft. and found 38 ft. of limy red rock, also 8 ft. of some blood red ending at 1820 ft., making 46 ft. of red rock in all. It is reported that some good ore was cut through but this work was done by a churn drill. At least 400 ft. of the formation was classified as Clinton. Well NO. 3, called Frankford Well, was bored by S. A. Hobson and associates in the northwest quarter of section 7, township 6, range 12, Franklin County. At 927 ft., it is supposed to have entered the Clinton; the log is as follows: Ft. Sandy limestone with reddish, high ferruginous argillaceous inclusions 10 Same growing more ferruginous................................ 18 Hematitic limestone......................................... 30 Same with slightly less iron.................................... 23 81

Jan 1, 1925

By D. J. Jr. McAdam

PART I.-OUTLINE OF INVESTIGATION, DESCRIPTION OF METHODS AND MATERIAL Previous Investigation of the Influence of Stress on Corrosion IN 1917 Haigh1 presented evidence that under simultaneous corrosion and cyclic stress metals may fail at lower stresses than if the corrosion is prior to the cyclic stress. In 1926 the author, while investigating the cooling effect of water on the fatigue resistance of metals, found that under these conditions steel specimens fail at stresses far below the endurance limit.2 (By "endurance limit" is here meant the fatigue limit obtained with specimens as free as possible from stress concentration and corrosive influences.) This led to an investigation (at the Naval Engineering Experiment Station, Annapolis, Md.) of the influence of cyclic stress on corrosion. This investigation maybe divided into three parts. The first part was a general survey of the conditions necessary to cause complete failure under corrosion and cyclic stress of relatively high frequency. The entire process by which metals fail under these conditions was-called "corrosion-fatigue." "Corrosion-fatigue limits" for a large number of metals were determined and the relationships of these limits to chemical composition, heat treatment and physical properties were established. The conclusion was reached that corrosion-fatigue is due to the accelerating influence of cyclic stress on corrosion. Results of this part of the investigation were presented in five papers.2-6 The second part of the investigation was a preliminary study of the influence of cyclic stress on corrosion. Each experiment was conducted in two stages. The first was a corrosion stage in which the specimen was corroded under cyclic stress; the second was a fatigue stage, in which the previously corroded specimen was tested (without further corrosion) to determine its fatigue limit. The difference between this fatigue limit and the endurance limit was used as a criterion of the "damage" due to

Jan 1, 1931

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By S. Weinig, E. S. Machlin

THE mechanism of the martensitic transformation has been the subject of a remarkable number of papers in recent years.' Because the task of evaluating all the available theories is a formidable one, the authors will confine themselves merely to the presentation of results of an experimental investigation of the habit orientation, lattice relations, magnitude and direction of average transformation shear strain, and orientation of subband markings for a single variant of the possible habit systems in an 11 pct Mo-Ti alloy. It is hoped that these data will assist in the establishment of a rigorous theory for the mechanism of the martensitic transformation. Experimental Procedure Specimen Preparation: A sample, approximately 1/2 x 1/4 x 1/4 in., was cut from a double arc-melted ingot composed of commercial-process A titanium and high purity molybdenum (nominally, 11 pct Mo). It was capsuled in evacuated Vycor at 10.-3 mm Hg subsequent to a double argon wash and homogenized for 48 hr at 1100°C. After a direct quench into H2O at room temperature, a large-grained specimen resulted, which, by X-ray diffraction and metallographic means, was subsequently shown to be in the body-centered-cubic phase, ß. Two adjacent, approximately perpendicular faces were polished and the ends of the specimen were ground parallel in a V-block. Fiducial lines were inscribed at 45" to the common edge of the polished surfaces in order that they would be perpendicular to the habit traces of the subsequently formed a plates.2 The specimen was then compressed between the ground ends in a Buehler press to stress induce the transformation ß to a'. Experimental Measurements: The habit-plane orientation, the orientation of subband markings, the orientation relation between the parent ß and the product a', and the transformation strain for the same plate were determined. To further establish the nature of the subbands, one surface was repol-ished and etched. The bands in the a' were still visible and were found to be optically anisotropic under polarized light. Back-reflection Laue patterns were obtained from the ß matrix and from a region comprising both a' plates and adjacent ß matrix (a Cu target was used). By superposition of the two X-ray diffraction patterns, it was possible to obtain a tentative orientation relationship between the two phases. This result was confirmed by a pattern taken after the specimen was rotated to make the basal-plane pole of the hexagonal a' phase strike the film. This necessitated cutting the specimen to expose the a' plate in the new position relative to the X-ray beam. Analysis of Experimental Measurements On the basis of the aforementioned X-ray patterns, the orientation between parent and product

Jan 1, 1955

By B. Chalmers, S. Wojciechowski

THE structure of the equiaxed zone of several A1-Cu samples mechanically stirred during unidirectional solidification was examined. The stirring was produced by rotary oscillation of the mold about its vertical axis.' It was found that in Some samples the structure is not of the same type over the whole of the equiaxed zone; it consists of regions with two different etching responses. Fig. 1 shows this structure in a Al-1 wt pct ku sample. The lighter etching regions with a coarse structure form something like a network and the darker etching regions with a finer structure can be observed as the continuation of the coarse structure inside this network. The difference in size and shape of the dendrite branches (they are rounded in the coarser structure) is similar to that found by Williamson and Chalmers in ice crystals solidified in undercooled water: when the amount of undercooling was small, the ice crystals were more rounded and coarser than these solidified with a larger amount of undercooling.' It seems justified to conclude that the observed structure resulted from solidification under different thermal conditions: the coarser structure solidified first out of the "purer" liquid and with a smaller amount of undercooling and the finer was formed later out of solute-enriched liquid under conditions of much more rapid heat extraction. A considerable change in the heat flow conditions at the later stages of solidification can be easily understood by taking into account that the coarser crystals form a continuous network and the amount of trapped liquid is relatively small; hence the contribution of latent heat is much smaller in the later stages of solidification. The difference in structure and etching characteristic reflects a difference in composition between these two regions. It was found that the darker etching re- gions are harder (30.4 to 31.3 HV5) than the lighter etching ones (25 to 26 HV5). A similar type of structure was found in a A1-4 wt pct Cu sample grown by Czochralski method. Fig. 2 shows the structure in the lower part of a sample grown slowly and then decanted by a rapid removing of the sample from the melt. In a few places trapped liquid solidified in the same manner as in the sample shown in Fig. 1.

Jan 1, 1968

By R. F. Mehl, C. E. Birchenall

SINCE Maxwell1 first considered the self-diffusion process in 1872 its importance in the kinetic theory of matter has been recognized. Until the discovery of isotopes in 1913, a direct measurement of this quantity seemed impossible. The only information that could be gathered indirectly was for gaseous systems for which the kinetic theory was well developed. When methods of direct observation be-came available, investigations on self-diffusion were carried out in condensed phases. In metals these data are presumably of potential importance in the study of recovery, recrystallization, creep, sintering, and related phenomena. Following the pioneer work of Von Hevesy2 and his collaborators, who determined the rate of self-diffusion in lead with the naturally occurring thorium B isotope, several metals have been investigated. Pb, Ag³, Au.6,5, and Cu6,7,8,9 are examples of isotropic crystals existing in only one phase modification. Anisotropy of diffusion has been demonstrated in Bil6 and Znll. This paper is a study of a single metal in two allotropic forms and also of self-diffusion in a body-centered cubic lattice. Despite the fact that the measurements in each of the papers cited on self-diffusion in copper seem to be internally consistent to about 10 to 15 pet, the curves reported by different authors differ by factors of 2 to 4 at the same temperatures. This uncertainty may account, in part, for the failure to establish a successful correlation between the self-diffusion rates and other physical characteristics of the metals. No satisfactory theory of metallic self- diffusion has as yet been proposed to account for all the existing data and to permit estimation in other metals. Experimental Part: Two units of radioactive iron were used in these experiments, each a mixture of Fe53 and Fe59 (12). Fe53 decays by K electron capture and the emission of an X ray with a half life of about 4 years. Fe59 emits two beta spectra, one with a maximum energy of 0.26 Mev, the other 0.46 Mev, and gamma rays of 1.1 and 1.3 Mev, with a half life of about 44 days. They were present in nearly equal concentration initially. The composite half life started at about 50 days and increased as the Fe59 decayed, leaving Fe55 relatively more abundant. After aging a year, the half life was too long to measure significant decay in a month. The absorption properties also changed with time. Because of the importance of the absorption coefficient in the diffusion calculations, it was necessary to determine this quantity frequently over the period during which these experiments were carried out. This correction was unsuspected at the time of publication of notesl3 on this work and accounts for the discrepancy in alpha iron and for part of the discrepancy in gamma iron.* * The data in the present paper supersede those given in the notes entirely. In one note the scale of log D was inadvertently reversed. In addition to the correction for the drift in absorption coefficient, the D values for gamma iron at low temperatures were high owing to insuficient correction for diffusion occurring during heating and cooling through the high temperature part of the alpha range at a rate much slower than that employed in the runs reported here. The high temperature alpha rates are much higher than the low temperature gamma rates and correspond to large equivalent times at these temperatures. These experiments were discarded and new measurements taken. Independent experiments with the same activity units indicated a radioactive contaminant in the iron, but exhaustive attempts to isolate and identify it chemically failed. These experiments? indicate † These experiments will be discussed in a later publication from this laboratory. that the contaminant represented only a trace of little importance in the diffusion results. The active iron was plated from an iron chloride solution. Enough of the solution was dropped on a 1% in. square of filter paper to wet it thoroughly.

Jan 1, 1951

By Reynold Q. Shotts

Data are presented which show that fractions of varying densities-from the same coals are oxidized at different rates by nitric acid. From oxidation data, the approximate quantity of "bright" and "dull" components may be calculated. Definite relationships between oxidation rate and rank are shown for density fractions from at least two bituminous coals.

Jan 1, 1950

By F. A. Olson, J. S. Cho, M. E. Wadworth

An infrared study of the states of hydration of MgSO4 revealed a hitherto unreported metustable dehydration state in the temperature range just below that of the stable anhydrous salt. Infrared, thermogvavimetric, and X-ray studies indicated that the state had bisulfate and hydroxide characteristics. A formula fitting all of the experimental evidence is hydrogen-bonded Mg(OH)HSO4, or possibly the chemically equivalent 1/2 Mg(HSO4)2. Mg(OH)2 Infrared spectra of the 7, 6, 1, and OH2O states of hydration are given as well as the spectra of the newly found state which is called the bisulfate state in this paper. Thermogvavimetric studies as a function of water-vapor pressure gave an enthalpy value of 16 cal per mole, and 25 eu for the conversion of the bisulfate state to that of the anhydrous salt. The free energies of the transition varied from 1.76 to 0.18 kcal per mole as the transition temperature varied from 279° to 336°C. The bisulfate state is believed to be of importance in catalytic dehydration phenomena using MgSO4 and may be of interest because of properties in sulfating reactions differing from those of the monohydrate. Also, an analogous state may exist as a hydration state of other sulfates. ANHYDROUS magnesium sulfate is a catalyst with a high degree of specificity for the dehydration of secondary alcohols.1'2 The only product obtained at the usual operating temperature range of 360" to 400°C other than the corresponding olefin is water. Thus, the bonding of water to the anhydrous salt as well as an understanding of the hydration states of MgSO4 became of interest in attempting to understand the catalytic mechanism better. In the process of this study using infrared, X-ray, and thermogravimetric analyses a dehydration state not previously reported was found. Proof of its existence, the nature of the state, and its role, if any, in the catalytic mechanism then became of interest. This paper is concerned principally with the first two aspects of this problem. Magnesium sulfate forms many hydrates, of which the monohydrate and heptahydrate (Epsom salts)3 are most important. Other hydrates4 are known with 1-1/4,5 l-1/2, 5 2, 4, 5, 6, and 12 H2O's. The hydrates with 1-1/4, 1-1/2, 2, 4, and 5 HzO's are unstable. The anhydrous salt is very stable thermally and has a strong affinity for water. It can be heated without additional decomposition to about 800°C.' At 900°C noticeable decomposition takes

Jan 1, 1964