Search Documents

By J. L. Taylor, Pol Duwez

THE present knowledge of the Ti-Al system is limited to the portion of the diagram extending from pure aluminum to the intermetallic compound TiAl3' A preliminary investigation of the titanium-rich Ti-A1 alloys revealed that the solubility of aluminum in titanium is quite extensive and that the transformation temperature of titanium is raised by alloying with aluminum. From an X-ray diffraction study of alloys containing up to 75 atomic pct Al (TiAl3), the phase boundaries at 750°C were located as follows: the a titanium solid solution extends from 0 to about 36 atomic pct Al, a two-phase region exists from 36 to 46 atomic pct Al, and an intermediate phase of varying concentration extends from 46 to 62 atomic pct Al. The purpose of the present paper is to describe the crystal structure of this new phase. The alloys were prepared by melting in a helium arc furnace on a water-cooled copper plate, using a furnace essentially the same as that described in ref. 2. The titanium metal was of the iodide type furnished by the New Jersey Zinc Co., and a piece of pure aluminum (99.99 pct) was obtained through the courtesy of the Aluminum Co. of America. After melting, the samples, weighing approximately 5 g, were sealed in evacuated fused silica tubes and homogenized for 4 hr at 1000°C. The specimens were then held for 10 days at 750°C and rapidly cooled to room temperature. Filings were then taken from each sample, sealed in evacuated vials, annealed at 750°C for 4 hr, and rapidly cooled to room temperature by quenching the vials in water. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using K copper radiation filtered through a nickel foil. Structure Determination The X-ray diffraction patterns of the alloys containing 46, 50, 55. 60, and 62 atomic pct Al were identical, except for a slight shift in the positions of the reflections. The alloy containing 55 atomic pct Al was chosen far structure determination. The powder pattern contained 37 reflections and the a, doublets were well resolved in the back-reflection range. The relatively small number of reflections and the sharpness of the pattern were considered as an indication of a simple atomic arrangement in a relatively small unit cell of high symmetry, and an attempt was therefore made to solve the structure without single crystal work. A satisfactory fit was found on a large scale Hull-Davey tetragonal chart for an axial ratio of approximately 1.45. All the reflections were readily indexed and the tentative unit cell dimensions were computed to be a - 2.81 kX, c - 4.07 kX, and c/a = 1.448. The indices (hkl) and the values of d and sin2 A are given in Table I. The agreement between observed and computed sin2 is quite satisfactory. Once the unit cell was known, the details of the structure were readily found. First, it is obvious that the number of atoms per unit cell cannot exceed two, since more than two atoms would lead to a density greater than that of pure titanium. The next logical step is to assume that the two atoms occupy the corner and center of the cell. If this assumption is correct, the structure may be described as follows: space group D1, - P 4/mmm; one titanium atom in a: 000; one aluminum atom in d: 1/2 1/2 1/2: and no extinctions. Assuming this structure to be the correct one. intensities were computed by means of the usual equation: sin2 0 cos 0 where F is the structure factor; 8, the Bragg angle. and p, the multiplicity factor. The calculated values of intensities are compared in Table I with the visually estimated intensities. The agreement is quite satisfactory and the structure is therefore confirmed. The crystal structure of TiAl just described is the same as that of AuCu ordered. The AuCu ordered

Jan 1, 1953

By Thomas F. Torries, George H. K. Schenck

Crushed and broken stone is used directly in construction as an aggregate and accounts for about half the value and two-fifths of the quantity of natural aggregates consumed in the United States. Sand and gravel provide most of the balance of aggregates except for some lightweight materials such as pumice and expanded shale. Conditions necessary for production of crushed stone from a deposit are : 1) Quality-should pass rigid specifications for strength and durability. 2) Cost-low average total delivered cost. Construction aggregates are hard, essentially inert materials suitable for being formed into a stable mass either (1) by the addition of cementing or binding materials that produce a concrete or (2) by compaction or by natural weight to produce a road base or foundation. Aggregates usually provide about 80 to 100% of the material volume of the construction masses in which they are used. The construction industry utilizes as aggregates about 70% of all crushed stone produced in the United States according to statistics provided by the U.S. Bureau of Mines (USBM) , [Table 1], using definitions as shown below. Nonconstruction uses of crushed stone, [Table 2], are included elsewhere in Industrial Minerals and Rocks because such uses require the special physical or chemical characteristics which are discussed in those chapters.

Jan 1, 1975

By Marion Rice

THE copper-mining district of Jerome, Ariz., is of such economic importance that the following brief notes may be of interest. The ore deposits are said by Ransome1 to be pre-Cambrian, and are contained in the pre-Cambrian schists of the region. In the vicinity of the mine (the United Verde) the schist stands nearly vertical .and strikes a little west of north. At least three varieties are distinguishable-(1) a green rock, schistose, on its margins but grading into massive material, which is evidently an altered dioritic intrusive; (2) a rough gray schist with abundant pheno-crysts of quartz, apparently an altered rhyolite; and (3) a satiny, greenish gray, very fissile sericitic schist that may be a metamorphosed sediment. The ore occurs in varieties (2) and (3), the main belt of dioritic rock (1) lying just west of the orebodies. The ore is said to follow as a rule the layers of fine sericitic schist. T. A. Rickard2 says that the ore at the United. Verde Extension mine is found at the contact of diorite and schist, that both diorite and ore are earlier than the regional metamorphism, and that the quartz porphyry (" rhyolite" of Ransome) is of post-Cambrian age.

Jan 9, 1918

By P. A. Tucker, T. B. Rhinehammer, D. E. Etter, J. E. Selle

The Ce-Cu phase diagram was investigated by differential thermal analysis and rnetallography. Two congruent melting compounds, CeCu2 (817°C) and CeCua (938°C), and three incongruent cornpounds, CeCu (516°C), CeCu, (796°C), and CeCu, CERIUM and copper have been suggested as possible diluents in a liquid-plutonium fueled reactor. As part of the determination of the Ce-Cu-Pu ternary phase diagram, a review Of the Ce-Cu system (798°C), are present in this system. Eutectics exist at 28 at. pct Cu (424°C), 74 at. pct Cu (756°C), and 91 at. pct Cu (876°C). The purity of the cerium used has an important effect on the results obtained by differential thermal analysis. was considered necessary. Previous work by Hanaman was conducted with relatively impure metal: 96.7 pct Ce with 2.5 pct other rare earths and 0.5 pct Fe as major impurities. The metal had a melting point of 715°C as compared to the melting point for pure cerium of 804°C as reported by Spedding and Daane.2 Results presented in this work were obtained primarily by differential thermal analysis (DTA) and metallographic examination of slow-cooled or quenched samples.

Jan 1, 1964

By Horace Pops, Jorge E. Kittl

In a recent study' of the martensitic transformation of Cu-Zn ß-phase alloys, it was noted that the MS temperature at the surface was raised due to the loss of zinc by volatilization. It seems likely, therefore, that the MS temperature may serve as a guide for the measurement of composition. From a knowledge of the dependence of the transformation temperature on composition, 2 it should be possible to detect variations in zinc content which are less than 0.1 at. pct by measuring the MS temperature throughout the sample. It is unlikely that an electron microprobe analysis could detect accurately such small zinc losses because the presently accepted limits of accuracy of the micro-probe analysis in simple ternary systems are of the order of 2 to 5 pct of the amount present.3 In the present study, a composition gradient was produced by precipitating the a primary solid solution, and reheating for a very short time within the ß-phase field. The nominal composition, in atomic percent, of the ternary ß-phase alloy used, 64.2 Cu, 34 Zn, 1.8 Si, was selected because it had an MS temperature of +4°C, thereby simplifying the experi-

Jan 1, 1968

By C. F. Smart

The heat treatment of the bronze composed of 88 per cent. copper, 10 per cent. tin, and 2 per cent. zinc, has been investigated by H. S. and J. G. S. Primrose,' and also by the U. S. Bureau of Standards.2 The results obtained by H. S. and J. G. S. Primrose on dry-sand castings subjected to reheating followed by air cooling, or by quenching in water, are shown in Figs. 1 and 2. The values for tensile strength have been converted from tons per square inch to pounds per square inch. Figs. 3 and 4, have been plotted from values obtained by the Bureau of Standards on material of the same composition and treatment. Both investigations show that the ductility of the cast bronze is improved by heating to 700' C. and cooling in air, the strength not being impaired by this treatment. They are not in agreement, howevcr, as to the effect of quenching, Messrs. Primrose reporting a decrease, and the Bureau of Standards an increase, in both strength and ductility when the cast bronze is heated to 600' or 700' C. and quenched. The present investigation was undertaken to study the effect of annealing followed by different rates of cooling, and, in particular, the

Jan 1, 1921

By G. P. Pilling

The use of magnetic ore in the blast furnace is a subject of increasing importance. The end of the deposits of lake ore is in sight, although not imminent, and unless some new field is discovered, the use of magnetites will be an increasing factor in the iron production of the country. Enormous deposits of magnetic ore in the country that have been practically untouched contain ore of sufficient richness and purity to prolong materially our ore supply without extensive importation of foreign ores. Magnetic ores can be divided into three general classes: Fine un-sintered, or raw ore; raw lumpy ore; fine ore that has been sintered. Fine Unsintered Ore Typical analysis and screen test of this class of ore from the Adirondack region is as follows: Per Cent. SCREEN TeST pER Cent. Fe.................... 58.00 Remaining on 4 mesh........... 7.50 SiOz.................. 7.50 Through 4 on 8 mesh........ 13.75 Al,O,................. 1.60 8 on 10 meah........ 3.75 Baseg................. 2.77 10 on 20 mesh........ 22.50 P.................... 1.00 20 on 40 mesh........ 27.50 Mn................... 0.13 40 on 60 mesh........ 2.50 S..................... Trace 60 on 80 mesh........ 10.00 80 on 100 mesh........ 2.50 100 mesh........ 10.00 100.00

Jan 1, 1923

By G. P. Pilling

The use of magnetic ore in the blast furnace is a subject of increasing importance. The end of the deposits of lake ore is in sight, although not imminent, and unless some new field is discovered, the use of magnetites will be an increasing factor in the iron production of the country. Enormous deposits of magnetic ore in the country that have been practically untouched contain ore of sufficient richness and purity to prolong materially our ore supply without extensive importation of foreign ores. Magnetic ores can be divided into three general classes: Fine un-sintered, or raw ore; raw lumpy ore; fine ore that has been sintered. Fine Unsintered Ore Typical analysis and screen test of this class of ore from the Adirondack region is as follows: Per Cent. SCREEN TeST pER Cent. Fe.................... 58.00 Remaining on 4 mesh........... 7.50 SiOz.................. 7.50 Through 4 on 8 mesh........ 13.75 Al,O,................. 1.60 8 on 10 meah........ 3.75 Baseg................. 2.77 10 on 20 mesh........ 22.50 P.................... 1.00 20 on 40 mesh........ 27.50 Mn................... 0.13 40 on 60 mesh........ 2.50 S..................... Trace 60 on 80 mesh........ 10.00 80 on 100 mesh........ 2.50 100 mesh........ 10.00 100.00

Jan 1, 1923

By E. T. Dumble

THE development in the Gulf Coastal Plain for the year 1923 was entirely devoid of any spectacular feature and was considerably less than that of 1922. No large fields were discovered and the principal advances lay in the extension of the old fields and the finding of a new dome and other possible producing structures, which, however, so far, have given only small wells. While the production of some fields, such as those at Hull and Orange, was materially increased at times by comparatively large wells, the output as a whole shows a marked decrease over that of the preceding year. TABLE 1.-Production by Fields in Gulf Coastal Plain in 1923 FIELD BARRELS FIELD BARRELS Anse La Butte 16,942 Jennings 212,376 Barber's Hill 172,660 Markham 39,290 Batson 391,857 North D ayton 74,983 Big Hill (Jefferson County) 13,853 Orange 5,311,995 Blue Ridge 332,445 Pierce Junction 332,565 Damon Mound 822,355 Richmond (Big Creek) 17,545 Edgerley 176,964 Saratoga 700,661 Goose Creek 6,251,761 Sour Lake 2,091,961 High Island 19,018 Spindletop 309,315 Hull... 7,732,139 Vinton 2,134,430 Humble 2,449,744 West Columbia 6,598,589 36,203,448

Jan 3, 1924

By C. B. Daellenbach, T. D. Tiemann

The prevention of quartz flotation by chelation of activating ions with the tetrasodium salt of EDTA in oleic acid flotation was investigated using a small vacuum flotation cell. It was found that flotation of quartz could be entirely suppressed in the presence of activating ions during complete flotation of hematite. It was further shown that the concentration of activating ions liberated from Wisconsin Gogebic taconite is sufficient to float quartz in an oleic acid system. Large tonnages of low grade siliceous iron ores occur on the iron ranges of the Lake Superior district. Although the lower grade nonmagnetic types are currently not of economic importance, they constitute a large future potential source of iron and steel, and hence have been the subject for extensive research on their beneficiation. TACONITES Of particular interest to the Dept. of Minerals and Metals Engineering at the University of Wisconsin have been the low grade nonmagnetic taconites of the Wisconsin Gogebic Range. These occur as five members of the iron formation and have been described in detail elsewhere.' Essentially they consist of an intimate mixture of hematite, goethite and quartz, with minor amounts of siderite, magnetite, iron containing silicates, and manganese minerals. A typical mean analysis based on the Bureau of Mines analyses' is: SiO2-52.50%, Fe2O3-43.40%, (Fe-30.38%), A12O3-1.15%, P2O5-0.07%, Mn2O3-0.29%, CaO-0.07%, (S-0.03%), Loss on ignition-2.00%. The quartz in these ores is of a microcrystalline variety,2 and so intimately associated with the iron oxide minerals that extremely fine grinding, in the order of minus 325 mesh, is required for liberation. During grinding and subsequent flotation, the concentration of quartz activating ions in the pulp becomes sufficiently high to activate quartz which floats along with the iron minerals in the presence of oleic acid. cook3 and co-workers concluded that oxidized iron ores released appreciable quantities of quartz-activating ions in water pulps. This is shown to be true in the present investigation. As a matter of fact, application of this phenomenon, as well as the intentional addition of activating calcium ions, is made use of in the an ionic flotation of silica from the iron oxide minerals.4,5 In view of the above, it becomes almost impossible to effect a sharp separation of quartz in the oleic acid flotation of the iron oxide minerals from these taconites, even with satisfactory liberation. This fact led to the current investigation to find a means of linking the activating ions with a chelating agent. The aim was to establish basic data for the quartz-water-oleic acid system which might not only be applicable to iron ores, but also to the flotation of other siliceous ores as well. EXPERIMENTAL METHODS Vacuum Flotation Cell: The vacuum flotation used in this investigation is similar to that used by previous investigators.6,7,8 The cell consisted of a 100 ml graduated cylinder with the lip removed. Vacuum from a water aspirator was applied to the cell through a trap; suitable tubing, and a rubber stopper inserted in the top of the cell. Constant absolute pressure was maintained by means of a manometer connected to the trap with a tee. Flotation: The required amount of activating ion solution was pipetted into a beaker. This was then diluted to 99.0 ml with water having a pH below that desired for the test, or so adjusted with HC1. After addition of 1.0 ml of oleic acid solution (2.0 mg oleic acid per ml), the pH was readjusted to the desired value with NaOH, and the entire solution transferred to the cell containing 1.5 gm of quartz. After vigorously agitating the cell and its contents for 2 min, the vacuum was applied to the cell and the estimated degree of flotation observed for a 3-min period. Activating ions studied included Ca++, Mg++, Al+++, and Fe+ + + added as chloride solutions. In addition,

Jan 1, 1964

By K. D. Jacob

ALL types of commercial phosphate rock produced throughout the world contain fluorine in quantities ranging from approximately 0.4 to 1.3 per cent in the Curacao and Christmas Island phosphates to 3.1 to 4.2 per cent in the phosphates of the United States and North Africa1. For a given type of rock, the fluorine content is usually roughly propor-tional to the phosphorus content. SIGNIFICANCE OF FLUORINE IN PHOSPHATE ROCK On the basis of chemical and X-ray diffraction studies, Hendricks and co-workers2 concluded that fluorapatite, Ca10F2(P04)6, is the essential phosphatic constituent of the commercial types of domestic phosphate rock. On the other hand, Bredig and co-workers3 have recently advanced the opinion, also based on X-ray diffraction studies, that the mineral phosphates usually contain carbon dioxide in the apatite lattice, and that the phosphate rocks of. the United States are really fluorcarbonate apatites. However, the domestic types of phosphate rock do not seem to differ greatly from coarsely crystalline fluorapatite in their behavior toward chemical reagents in general, and for the purpose of this paper it will suffice to consider fluorapatite as being the essential phosphatic constituent of these types of rock.

Jan 1, 1936

By J. J. Bikerman

In a recent study' of the martensitic transformation of Cu-Zn ß-phase alloys, it was noted that the MS temperature at the surface was raised due to the loss of zinc by volatilization. It seems likely, therefore, that the MS temperature may serve as a guide for the measurement of composition. From a knowledge of the dependence of the transformation temperature on composition, 2 it should be possible to detect variations in zinc content which are less than 0.1 at. pct by measuring the MS temperature throughout the sample. It is unlikely that an electron microprobe analysis could detect accurately such small zinc losses because the presently accepted limits of accuracy of the micro-probe analysis in simple ternary systems are of the order of 2 to 5 pct of the amount present.3 In the present study, a composition gradient was produced by precipitating the a primary solid solution, and reheating for a very short time within the 0-phase field. The nominal composition, in atomic percent, of the ternary ß-phase alloy used, 64.2 Cu, 34 Zn, 1.8 Si, was selected because it had an MS temperature of +4°C, thereby simplifying the experi-

Jan 1, 1968

By M. Metzger, J. Intrater

IN the large number of important studies on high-purity aluminum (e.g., recrystallization and grain growth, creep, internal friction), it does not seem to have been generally recognized that the iron content, despite its very low figure, has a strong influence on a number of properties. In part, its influence is due to the very low solubility of the Fe-A1 6 phase. For aluminum of about 99.99 pct purity, the iron content may be 0.001 to 0.004 pct. For values in this range, a second phase will be present below 410" to 480 °C. This was determined by extrapolation of a log solubility vs inverse temperature plot of the solid solubility data of Edgar.' One consequence is the inhibition of grain coarsening below the solubility limit. This is shown in Table I, which gives, for three iron contents, the annealing temperature required for the absence of grains smaller than 1/2 mm average diameter together with the minimum temperature for the presence of some grains larger than 2 mm diameter. The specimens were 1/4x 1 1/2-in. strips cut from hard-rolled 1/16-in. sheet supplied by the Aluminum Co. of America.

Jan 1, 1954

By R. R. Morral, F. M. Krill, K. T. Aust

THE occurrence of twins in aluminum ingots cast under certain conditions has been well established. For instance, Herenguel and Lacombe1,2 have observed a twinned columnar structure in 99.5 and 99.9 pct Al, solidified by continuous or semicontinuous casting. The structure, which they termed "basaltic," appears in the form of elongated crystalline fibers of alternating luster. Herenguel and Lacombe2 found sections of flat crystalline plates composed of twin crystal plates, in which the twin plane (111) and a [I121 direction contained in the twin plane are parallel to the principal heat gradient. This orientation relationship is different from the usual orientation texture observed in cast face-centered cubic metals, where the [100] direction is approximately parallel to the long columnar axes lying in the direction of growth." A large amount of twinning has also been observed by the present authors in semicontinuous cast aluminum of 99.2 pct purity, Fig. 1. Mondolfo4 has suggested that the twinned cast structure forms by a deformation twinning process as the result of uneven cooling stresses within the ingots. This suggestion appears to be inconsistent with the large amount of twinning observed in the semicontinuous cast ingots and with the large difference of dendritic

Jan 1, 1953

By S. Skowronski, K. W. McComas

Page Purpose of investigation.....................'. 354 Details of experiments........................ 357 Experiment Series No. 1, melting copper containing chlorine under carbon dioxide............................... 358 Experiment Series No. 2, melting hydro-electric cathode copper drillings under air................................ 362 Experiment Series No. 3, melting hydro-electric cathode copper drillings under furnace gases............................ 363 Summary.............................. 364 Purpose of Investigation Since cuprous chloride melts at 418' C., boils at 954' C. to 1032' C.,' and is known to be volatile at a much lower temperature, the presence of chlorine in any form in or on copper to be melted has always been looked upon by copper refiners as a possible source of serious copper loss. Although this fact has been known for some time, the copper literature contains little or no information regarding it and the field seems never to have been properly investigated from a metallurgical standpoint. According to Greenawalt,2 cupric chloride, CuCl2, when ignited gives cuprous chloride; therefore cuprous chloride is always formed when copper enters into reaction with chlorine at a high temperature. Cuprous chloride melts somewhat below a dull red heat, and does not volatilize in closed vessels, even if strongly heated, but if heated in the air it goes off as a white vapor, Hofman3 gives the melting point of cuprous chloride

Jan 1, 1919

By A. L. Field, P. H. Royster

The first report on the slag viscosity work of the Bureau of Mines was made by one of the authors1 in 1916. It was concerned chiefly with the method of measurement. A paper2 on this phase of the work was presented to the Institute in February, 1917, and a similar paper3 was communicated to the Faraday Society. PuRpose and Scope of the Slag Viscosity Tables Following the development of a suitable method, the next step in the investigation was the measurement of slag viscosity over a wide range of temperature and composition, and the arrangement of this experimental data in the form of tables for the use of the blast-furnace operator. It is believed that this information, if used intelligently, should help the operator to reduce losses in production caused by off-grade pig iron, to improve fuel economy, to promote operating efficiency, and to extend present-day practice to meet the increasing need of smelting lean and complex ores. In the experimental part of the work it was carly, observed that the temperature-viscosity relations of a slag were determined, for practical purposes, by the relative proportions of the three major constituents, lime (CaO), alumina (Al2O3), and silica (SiO2), provided the percentage

Jan 1, 1918

By E. T. Dumble

THE development in the Gulf Coastal Plain for the year 1923 was entirely devoid of any spectacular feature and was considerably less than that of 1922. No large fields were discovered and the principal advances lay in the extension of the old fields and the finding of a new dome and other possible producing structures, which, however, so far, have given only small wells. While the production of some fields, such as those at Hull and Orange, was materially increased at times by comparatively large wells, the output as a whole shows a marked decrease over that of the preceding year. TABLE 1.-Production by Fields in Gulf Coastal Plain in 1923 FIELD BARRELS FIELD BARRELS Anse La Butte 16,942 Jennings 212,376 Barber's Bill 172,660 Markham 39,290 Batson 391,857 North D ayton 74,983 Big Hill (Jefferson County) 13,853 Orange 5,311,995 Blue Ridge 332,445 Pierce Junction 332,565 Damon Mound 822,355 Richmond (Big Creek) 17,545 Edgerley 176,964 Saratoga 700,661 Goose Creek 6,251,761 Sour Lake 2,091,961 High Island 19,018 Spindletop 309,315 Hull 7,732,139 Vinton 2,134,430 Humble 2,449,744 West Columbia 6,598,589 36,203,448

Jan 3, 1924

By J. A. Herbst, G. E. Agar

Beginning with the second paragraph in the second column of page 148, this paper should read: The Reynolds number in Fig. 6 was calculated from the inlet diam and it is evident from the graph that above NR = 5000 the value of K2 is as it should be, a constant. The data10 shown in Fig. 7 was obtained for fluids flowing in pipes of diam D with sharp edged orifices of diam d. To be consistent with the representation in Fig. 6 the Reynolds number was calculated with the orifice diam d. These two sets of data show similar patterns and the variation in the orifice coefficient C is believed to account for the variability of the cyclone coefficient K2. The values of C given in Table IV are derived from K2 by conversion of units. C more nearly represents an equivalent orifice coefficient for a cyclone. Armstrong1' showed that data reported by Chaston 12 and Elcox13 yielded values for C of 0.24 and 0.27, re- spectively, Dahlstrom's4 data gives a value of 0.22. As a consequence of the variability of the cyclone coefficient some caution must be exercised in substituting for Q in the split size equation.

Jan 1, 1967

By C. F. Smart

THE heat treatment of the bronze composed of 88 per cent. copper, 10 per cent. tin, and 2 per cent. zinc, has been investigated by H. S. and J. G. S. Primrose,1 and also by the U. S. Bureau of Standards.2 The results obtained by H. S. and J. G. S. Primrose on dry-sand castings subjected to reheating followed by air cooling, or by quenching in water, are shown in Figs. 1 and 2. The values for tensile strength have been FIG. 1.-EFFECT OF QUENCHING ON DRY SAND CASTINGS (H. S. AND J. G. S. PRIMROSE.) converted from tons per square inch to pounds per square inch. Figs. 3and 4, have been plotted from values obtained by the Bureau of Standards on material of the same composition and treatment. Both investigations show that the ductility of the cast bronze is improved by heating to 700° C. and cooling in air, the strength not being impaired by this treatment. They are not in agreement, however, as to the effect of quenching, Messrs. Primrose reporting a decrease, and the Bureau of Standards an increase, in both strength and ductility when the cast bronze is heated to 600° or 700° C. and quenched.

Jan 9, 1919

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