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By W. J. Parton

THE efficient recovery and preparation of small sizes of anthracite called No. 4 Buckwheat (3/3 2 by 1/3 2 in.) and No. 5 Buckwheat (1/3 2 in. by 0), present a difficult problem to the anthracite operators. In many instances preparation of these sizes, particularly No. 5 anthracite, is extremely inefficient. In many of the older preparation plants, inadequate facilities, and often none at all, were provided as an integral part of the plant for cleaning this fine anthracite. Consequently, much of the material smaller than s, 32 in. was discarded. As the demand for these sizes increased, facilities for preparing the fine sizes were often crowded into existing structures with consequent sacrifices of capacities and efficiency. In addition to this condition, the methods of preparing the finest sizes are being developed in an attempt to improve their efficiencies. Because the demand for small sizes of anthracite still is increasing, many operators would benefit by investigating and improving the cleaning equipment employed on these sizes.

Jan 1, 1949

By M. M. Fine

Normally the U. S. produces less than 10 pct of its annual manganese requirement. About 95 pct of domestic consumption is used by the steel industry.' The strategic and critical nature of manganese has been recognized by its inclusion in the national stockpile and by intensified research directed toward cataloging and evaluating domestic manganiferous deposits. The USBM has participated in these activities for many years with field and laboratory studies to assess the extent and potential utilization of domestic manganese ores. One area of particular interest is in the vinicity of Batesville, Ark., where deposits have been mined since 1849 for both manganese and ferruginous manganese ores. Production is centered in Independence County, but deposits are also found in Sharp, Izard, and Stone counties in north-central Arkansas. Miser has described the geology and manganese mineralization in some detail.'. * "he rocks of the area are sedimentary, consisting of sandstone, limestone, shale, and chert. The two formations of greatest importance,' Fernvale limestone and Cason shale, are host rocks of the primary manganese mineralization. Through 1955 the district produced some 230,000 long tons of manganese ore (35 pct Mn or more) and 236,000 tons of ferruginous manganese (10 to 35 pct Mn).5 Most of the ore has been mined from deposits of manganese oxides in residual clays resulting from weathering of the two formations noted above. Concentration methods have been primitive, consisting for the most part of washing. hand picking, and jigging. A significant accomplishment in the district in recent years was the USBM recognition and investigation of the huge manganese potential represented by unaltered Fernvale limestone. systematic reconnaissance of manganiferous limestone and other occurrences has been in progress since 1953 to delineate the extent and tonnage of manganiferous materials. Results of that survey have appeared in two recent publications,1-5 which ascribe to the district an inferred reserve of 166 million long dry tons at a grade of 5 to 6 pct Mn. Most of this was mancaniferous limestone with an estimated content of 5 pct Mn. Specifications: Beneficiation was carried out on a group of manganiferous limestones to develop a way to recover commercial-grade concentrate from this extensive resource. The following chemical specifications were established by the GSA for metallurgical manganese ore acceptable for delivery to the national stockpile: Size specifications were not considered, as it was assumed that the concentrates could be pelletized or sintered. Manganiferous Limestones: Of the 11 samples tested to date, six were taken by cutting vertical channels across beds of limestone outcrops. Diamond drilling through overlying barren chert into unex-posed limestone provided four samples, and the last was a churn drill sample. In general, the samples were dlrk, fossiliferous limestone containing small amounts of braunite, hausmannite, rhodochrosite, massive and micaceous iron and manganese silicates, quartz, barite, and glauconite. The braunite and other manganese oxides partly to completely replaced some of the calcite and fossil material. The calcite was generously stained with mangenese and iron oxides. Phosphorus was present in all samples as collophanite grains, calcium phosphate fossil replacements. or an unidentified manganese-bearing carbonate. The difficulty in separating this complex array of minerals was further complicated by a very intimate association. Although some manganese grains as large as Ik in. were noted, grinding to subsieve sizes would have been necessary to liberate the components. Figs. 1 and 2 are micrographs, at X100, of typical polished sections in which white areas are manganese. gray is gangue, and black areas are surface depressions. By comparison with the 100 mesh opening, it is seen that some of the grains are coarse enough to respond, perhaps to tabling or flotation, but many are obviously beyond the scope of ohysical processing. Partial chemical analyses of the eight samples that were ultimately amenable to concentration are presented in Table 1. BENEFlClATlON RESEARCH Tabling: To take advantage of the presence of sand-size grains, both jigging and tabling were considered at the outset. Jigging was largely ineffective, but tabling achieved a partial recovery from most samples. As an example, the surface material from Baxter Hill was crushed to —28 mesh, hydraulically classified, and the coarsest spigot fraction was tabled to yield a concentrate, middling. and tailing. The latter two were reground to pass 48 mesh, combined with the primary fines, re-classified, and retabled. The middling and tailing were again ground, this time to pass 150 mesh, and deslimed at 20µ in a 3-in. hydraulic cyclone. The cyclone underflow was returned to the table to reclaim a small amount of high-grade manganese. An interesting facet of the gravity concentration developed on certain samples in which braunite was the principal manganese constituent. Since braunite has a Mohs hardness of 6 to 6.5, while the host rock, limestone. is only 3, a differential size reduction took place during crushing, and the

Jan 1, 1960

By Albert Sauveur

MY FIRST paper dealing with the theories of the hardening of steel by rapid cooling was published in the Transactions of this Institute in 1896-30 years ago-under the title "The Microstructure of Steel and the Current Theories of Hardening;" hence, also, the title of the present paper. It was extensively discussed and was, I believe, one of the starting points of many subsequent papers and discussions of the same subject, discusssions which at times became almost violent and which led to the formation of different schools such as the "Carbonists" and the "Allotropists." Some of the older members of the Institute, who took part in the debate or who were interested observers, will, I am sure, have kept a vivid remembrance of it. The controversy gradually quieted down, apparently for lack of ammunition, without any side acknowledging defeat. Recently, however, interest in it has been revived through the claims of some that these vexed questions had at last been solved. In an effort to ascertain if possible the prevailing view of those best qualified to express an opinion a questionnaire was submitted to the following gentlemen: J. 0. Arnold Sir Robert Hadfield Edgar C. Bain W. H. Hatfield Carl Benedicks Samuel L. Hoyt N. Belaiew Kotaro Honda H. M. Boylston Zay Jeffries Harry Brearley H. Le Chatelier G. K. Burgess H. H. Lester William Campbell Francis F. Lucas H. C. H. Carpenter John A. Mathews Pierre Chevenard A. McCance P. Dejean Albert Portevin C. A. Edwards Walter Rosenhain F. Giolliti Bradley Stoughton G. Grenet F. C. Thompson Leon Guillet

Jan 2, 1926

Question 1—1s Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions. Especially in Limestone or Other Dense Rocks Discussion by: A. M. Bateman.........120 S. F. Kelly........... 125 C. H. Behre. Jr........118.123 G. B. Langford......... 123 T. M. Broderick.........121 H. E. McKinstry......... 116 R. H. Clarke.......... 123 D. H. McLaughlin........ 118 J. D. Forrester for M. H. Gidel . . 11.4 W. H. Newhouse......... 123 G. M. Fowler......112. 116. 121 R. H. Sales.......... 116 L. C. Graton..........121 Edward Sampson......... 122 R. D. Hoffman.........120 J. 8. Stevenson.......... 117 I. B. Joralemon.........121 L.B.Wright........... 112 Question 2—What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? Drscussion by: G. W. Bain....... 127 G. M. Fowler....... 131 C. H. Behre, Jr. ..... 131 L. C. Graton....... 128 J. S. Brown. ...... 126 G.. F. Loughlin...... 128 E. L. Bruce ....... 129 R. H. Sales........ 129 R. H. Clarke...... 130 A. K. Snelgrove....... 130 Question 3—Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? Discussion by: J. M. Boutwell...... 139 G. B. Langford..... 139 T. M. Broderick..... 138 . G. F. Loughlin...... 135 E. Y. Dougherty..... 137 R. H. Sales...... . 134 G. M. Fowler....... 132 F. A. Thomson..... 136 I. B. Joralcmon...... 132 Edward Wisser:..... 140 General s. F. Kelly................. . ...........145 References...............................146

Jan 1, 1941

Question 1—1s Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions. Especially in Limestone or Other Dense Rocks Discussion by: A. M. Bateman.........120 S. F. Kelly........... 125 C. H. Behre. Jr........118.123 G. B. Langford......... 123 T. M. Broderick.........121 H. E. McKinstry......... 116 R. H. Clarke.......... 123 D. H. McLaughlin........ 118 J. D. Forrester for M. H. Gidel . . 11.4 W. H. Newhouse......... 123 G. M. Fowler......112. 116. 121 R. H. Sales.......... 116 L. C. Graton..........121 Edward Sampson......... 122 R. D. Hoffman.........120 J. 8. Stevenson.......... 117 I. B. Joralemon.........121 L.B.Wright........... 112 Question 2—What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? Drscussion by: G. W. Bain....... 127 G. M. Fowler....... 131 C. H. Behre, Jr. ..... 131 L. C. Graton....... 128 J. S. Brown. ...... 126 G.. F. Loughlin...... 128 E. L. Bruce ....... 129 R. H. Sales........ 129 R. H. Clarke...... 130 A. K. Snelgrove....... 130 Question 3—Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? Discussion by: J. M. Boutwell...... 139 G. B. Langford..... 139 T. M. Broderick..... 138 . G. F. Loughlin...... 135 E. Y. Dougherty..... 137 R. H. Sales...... . 134 G. M. Fowler....... 132 F. A. Thomson..... 136 I. B. Joralcmon...... 132 Edward Wisser:..... 140 General s. F. Kelly................. . ...........145 References...............................146

Jan 1, 1941

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature microhardness of as-grown and annealed MoaC single crystals was measured on the (0001), {2110), and1012) planes using Knoop and Vickevs indenters at loads ranging front 25 to 1000 g. The orientatimz dependence of hardness with respect to crystal axes was also studied. The average random hardness of as-grown crystals was determined to be 1520 kg per sq nm. Annealing to 2000°C decreased. the average hardness by 150 units. An increase in hardness after annealing at 2200 ;C was noted. Optical and electron microscopy revealed slip and twin traces on all planes studied, as produced by mi-cvohavdness indentations. Basal (0001)(2i10) slip was determined to be the primary slip system and was substantiated by electron transmission microscopy. A secondary {1010)(2110) slip was produced by mi-crohardness indentations. The lattev also produced twinning- of the {10i2)[0001] type, as proven by electron diffraction. Electrical resistivity and elastic-modulus anisotropy were found and correlated with hardness anisotropy and Mo2C crystal structure. Elastic-modulus values were obtained by microhard-uess and ullrasonic methods. Bonding mechanism of Mo2C is discussed. ROOM-TEMPERATURE microhardness indentations are useful for studying hardness anisotropy, slip, and twinning in brittle materials. Slip has previously been produced in this manner in and WS~~.~ Recently, the authors5 reported slip of the {10i0)(11~0) type produced by high pressure and microhardness indentations on hexagonal TiBz (c/a = 1.066) single and polycrystals. This slip system was also reported by French and ~homas' and Taka-hashi and ~reise~ for hexagonal WC (c/a = 0.976) crystals. These results suggest that prismatic rather than basal slip is favored in hexagonal nonmetallic materials having a c/a ratio considerably less than the ideal (1.633). Buerger precession and cylindrical X-ray rotation patterns were previously' taken on cleaved sections of the Mo2C single crystals studied in this work. Th~y were found to be hexagonal MoaC with a. = 3.0233A, co = 4.7344A, and C/O = 1.5660. The latter ratio is close to that of the beryllium metal (c/a = 1.57), which slips primarily on the (0001) plane: but also slips on the (1010) planes.'0 ~irconium" (c/u = 1.59) and titanium12 (c/o = 1.59) deform mainly by slip on nonbasal planes which contain a close-packed direction. This is due to the fact that for these two metals the initial resolved shear stress for slip on the (10i0) prismatic planes is lower than that on the (0001) plane. The prominence of basal rather than prismatic slip in metals of high c/o ratios is shown by cadmium (c/a = 1.89), zinc (c/a = 1.86), and magnesium (c/a = 1.62) which deform mainly by basal slip. However, in case of the latter, by stressing magnesium crystals in tension or compression parallel to the basal plane, slip on (10i0) planes can also be produced.13 Several hardness values for polycrystalline Mo2C are reported in the literature: Biickle ' and Samsonov'~ give a value of 1800 and 1479 kg per sq mm, respectively, at a 100-g load; and Kieffer and Benesovsk~'~ report a value of 1950 kg per sq mm at a 50-g load. ~ott'~ reports a Vickers hardness value of 2000 kg per sq mm, with the load unspecified. A Rockwell A hardness value of RA = 88 has also been reported.'' In the present work, for comparison with single-crystal Mo2C hardness values, a Khnloo value of 1600 It 150 kg per sq mm was found on 99.6 pct pure and 99 pct dense hot-pressed Mo2C. This work was undertaken partly to explain the considerable differences in hardness values reported for polycrystalline Mo2C. EXPERIMENTAL The Mo2C single crystals investigated were prepared by a Verneuil-type process using an electric arc by the Linde Co. of the Union Carbide Corp.lg The largest specimens grown were boules 7 mm in diam by 40 mm in length. The crystals had an average density of 9.04 g per cu cm, with a Mo + C content of 99.8 wt pct. The major impurities were: 100 ppm each Na, Zr, and Ca; 85 ppm 0, 55 ppm Fe, and 10 ppm each Cr and Ta. The crystals were found to be carbon-poor, the average carbon content being 5.73 wt pct (stoichiometric value is 5.89 pct). The molybdenum content was found to be 94.08 pct, which is nearly stoichiometric. Electron-microprobe traverses of selected specimens were done with a Phillips-AMR microanalyzer. Thin-film and carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to optical and electron-optical studies, specimens were mounted in Lucite and polished on a vibratory polisher using diamond-paste grades ranging from 9-1 p and Linde A powder for up to 48 hr. Dilute nitric acid was used for thin-section polishing and chemical etching for 1-15 min. Electrical-resistivity measurements at room temperature were taken with a Rubicon bridge, using gold contacts. For hardness measurements, a Tukon Microhardness Tester Type FB with Knoop and Vickers indenters was used. Measurements were taken at loads ranging from 25 to 1000 g; however, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Indentations of cracking classes 1 and 2 only were considered for hardness determinations.20)21 (There are six cracking classes, ranging from "class 1" for a perfect inden-

Jan 1, 1967

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

NEW MEMBERS The following list comprises the names of those persons who became members during the period of July 10, 1917, to Aug. 10, 1917. ARNOT, STANLEY L., Engr., Plymouth Cons. Gold Mines; Ltd., Plymouth, Amador Co .2 Cal. BARRETT, LESLIE PARK, Asst. Geol.... Michigan Geological Survey, Lansing, Mich. BENNIE, JOHN WILLIS Gen'l. Mgr., Shannon Copper Co., Clifton, Ariz. BRINTON, OWEN FUGATE Mgr., Admiralty Zinc Co., Quapaw, Okla. BRODERMANN, JORGE, Civil Engr., Compania Minera San Francisco, Havana,Cuba. BROWN, RICHARD HENRY JR., Sales Engr., Ingersoll Rand Co., 300 N. Broadway, St. Louis, Mo. BROWN, STANLEY Chile Exploration Co., Chuquicamata, Chile. BUDDECKE, WILLIAM A Pres., Point Milling & Mfg., Co. Mineral Point, Mo. BURGESS, GEORGE K., Physicist and Chief, Division of Metallurgy, Bureau of Standards, Washington, D. C.

Jan 9, 1917

By O. J. Huber, P. D. Frost, H. A. Robinson

URANIUM is a (ß-stabilizing, eutectoid-forming element when alloyed with titanium. Udy and Boulger1 have reported that an alloy of 48.6 pet uranium in titanium retains ß-phase when quenched from the ß-region, while compositions of approximately 30 pet uranium transform to martensite during such quenching. Since the eutectoid reaction is rather sluggish, titanium-uranium alloys should be capable of being strengthened by the ß — a trans-

Jan 1, 1959

By J. S. Marsh, T. B. Winkler

THE past year, the first full one of peacetime production, proved that the process of beating swords into plowshares has increased in complexity in step with civilization. Further, judging by various remarks of our distaff departments, the crystal balls of certain radio and magazine oracles must have been cloudy, because we have been in formed from time to time that coveted items such as automobiles and refrigerators did not appear in great abundance. This seemingly extraneous matter is really not out of place here, however; the steel producer and the fabricator exist in a sort of symbiosis: the making of consumer goods produces scrap which is returned to the steelmaker who makes more steel, and so on and so forth. Thus, no abundance of automobiles, no abundance of scrap from this normal source; and other sources had been picked pretty clean during the war. To be short, so was scrap. Since the economy of the steel industry lean; as heavily upon iron from scrap as upon iron from ore, the statement on transformation of swords to plowshares follows. But this is not the whole story: after all, ingot production was a record for a peace year!

Jan 1, 1947

By Cyril Stanley Smith

BeTa brass (consisting of approximately equal atomic proportions of copper and zinc) exists as a random solid solution at high temperatures, hut at low temperature< an ordered structure is stable, with the copper and zinc atoms occupying alternate sites on the body-centered-cubic lattice. On cooling, ordering commences at a temperature of 450° to 470°C., depending on the composition. The degree of ordering progressively increases at lower temperatures until it becomes virtually complete at about 100°C. The electrical resistivity of the alloy illustrates the changes clearly (Fig. I). This type of reaction has been a favored subject for study by physicists. An excellent summary of the theory is to be found in a paper by F. C. Nix and W. Shock1ey.l All published data on electrical conductivity, specific heat and other properties agree in indicating that the ordering reaction in beta brass takes place so rapidly that it cannot be prevented or even retarded by quenching&apos; With most ordered alloys, cold-working induces disorder and

Jan 1, 1943

By Cyril Stanley Smith

BeTa brass (consisting of approximately equal atomic proportions of copper and zinc) exists as a random solid solution at high temperatures, hut at low temperature< an ordered structure is stable, with the copper and zinc atoms occupying alternate sites on the body-centered-cubic lattice. On cooling, ordering commences at a temperature of 450° to 470°C., depending on the composition. The degree of ordering progressively increases at lower temperatures until it becomes virtually complete at about 100°C. The electrical resistivity of the alloy illustrates the changes clearly (Fig. I). This type of reaction has been a favored subject for study by physicists. An excellent summary of the theory is to be found in a paper by F. C. Nix and W. Shock1ey.l All published data on electrical conductivity, specific heat and other properties agree in indicating that the ordering reaction in beta brass takes place so rapidly that it cannot be prevented or even retarded by quenching&apos; With most ordered alloys, cold-working induces disorder and

Jan 1, 1943

By Cyril Stanley Smith

BETA brass (consisting of approximately equal atomic proportions of copper and zinc) exists as a random solid solution at high temperatures, but at low temperatures [ ] an ordered structure is stable, with the copper and zinc atoms occupying alternate sites on the body-centered-cubic lattice. On cooling, ordering commences at a temperature of 450° to 470°C., depending on the composition. The degree of ordering progressively increases at lower temperatures until it becomes virtually complete at about 100°C. The electrical resistivity of the alloy illustrates the changes clearly (Fig. I). This type of reaction has been a favored subject for study by physicists. An [ ] excellent summary of the theory is to be found in a paper by F. C. Nix and W. Shockley.1 All published data on electrical conductivity, specific heat and other properties agree in indicating that the ordering reaction in beta brass takes place so rapidly that it cannot be prevented or even retarded by quenching. With most ordered alloys, cold-working induces disorder and

Jan 1, 1942

By Leslie Burris, J. C. Hesson

The diffusivity of uranium in liquid cadmium has been measured as a function of temperature by the capillary -bath technique. The diffusivity measurements were made at 4509 500°, 575º, and 650°C, over which temperature range the diffusivity of uranium varied from 1.3 to 2.3 x 10-5 sq cm per sec. The diffusivity of uranium in cadmium was less than that predicted by the Einstein-Stokes equation. VERY little information is available on the diffusivity of uranium in liquid metals. Bonillal has reported a single measurement of the diffusivity of uranium in bismuth. Measurement of the diffusivity of uranium in cadmium was undertaken, not only to supply data in an area in which a dearth of information exists, but also because of a need for this physical property measurement in connection with mass transfer studies now underway in the U-Cd system at Argonne National Laboratory. The capillary-bath method used in this work has been successfully used by other workers2"4 to obtain diffusivities in liquid metal systems. Although considerable experimental technique is required to obtain reliable diffusivity measurements, the basic information required is only that of temperature, capillary tube length, the initial and final compositions of the alloy in the capillary tube, and the composition of the bath into which the solute element is diffusing. From these measurements, diffusivities may be calculated using Fick&apos;s law. The diffusivity equations are presented in the Appendix. Equations which are often used to predict diffusivities in dilute solutions5 are the Einstein-Stokes equation: D= (kT)/(6pµr) and the Eyring equation: D = (?,kT/?y?zp), where D= diffusivity (sq cm per sec), k = Boltzman&apos;s constant, T= temperature ("K), p = viscosity (poises), r = radius of diffusing molecule or species (cm), and A,, Ay, and A, are the diameters of the diffusing molecule in the three axial directions. For round molecules, the Eyring equation gives values which are 37r times larger than the Einstein-Stokes equation. In this work, the experimental values were compared to the Einstein-Stokes equation. Experimental values of diffusivities in liquid metal systems usually lie between those predicted by the Einstein-Stokes and Eyring equations. The viscosity values for cadmium were obtained from the Liquid Metals Handbook.6 EXPERIMENTAL APPARATUS AND PROCEDURE The general procedure employed consisted of rapidly immersing in a molten cadmium bath containing a negligible amount of uranium a capillary

Jan 1, 1963

By W. G. Oldham

By monitoring the capacitance of abrupt p-n junctions it is possible to follow the motion of substitu-tional impurities. A p-n junction is formed by growth of silicon from an Al-Si alloy on an n-type silicon sutstrate at a temperature in the range 650" to 750°C. The diodes are etched and sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed to various temperatltres for 10 mm and the capacitance remeasnred. For very heavily doped diodes (-1019 per cm3) observable capacitance changes occur at neutron fluences of >1015 per cm 3. The results may be interpreted in seceral ways, the simplest of which is to assume simple vacancy diffiision with small impurity -racancy interaction (at the diffiision, i.e. annealing temperature of 700°C). In this interpretation it is found that a typical vacancy makes about 1024 jumps and travels about 10-5 cm before disappearing. The required effective annihilation center density is about 1016per cm3 . Estimates of the vacancy-impurity interaction can be made and the above numbers correctecl, but for arty reasonable assumptions the number of vacancy sinks connot be much reduced. ThE complete annealing of radiation induced defects requires that the vacancies and interstitials either recombine, travel to the surface of the crystal, or travel to an annihilation center, e.g., a dislocation or a precipitate. If the interstitial is ignored except as a possible vacancy annihilation center at low temperatures,* the motion of vacancies may be followed by monitoring the corresponding motion of substitutional impurities. pfister2 has measured the enhanced diffusion of impurities in an asymmetric shallow diffused silicon structure by optically monitoring the junction movement. In these experiments we monitor instead the capacitance of a heavily-doped deep symmetric p-n junction. The sensitivity for this method is several orders of magnitude higher than in Pfister&apos;s technique, mainly for two reasons: 1) the junction capacitance of a heavily-doped junction is sensitive to impurity movements in the Angstrom range* com- and 2) the junction may be far from the surface which is a major annihilation center for vacancies. THE EXPERIMENT A p-n junction is formed by the epitaxial growth of silicon from an A1-Si alloy on a silicon substrate at a temperature in the range 650° to 750°C. The technique used is the transport of an aluminum melt through a temperature gradient.4 A 10-mil thick aluminum disc is sandwiched between two silicon wafers and the assembly raised to about 650° C with a temperature gradient normal to the sandwich. After about 8 hr the upper (hotter) wafer has been entirely transported and deposited epitaxially on the substrate wafer. The substrate and overgrowth resistivity are measured with a 4-point probe. The as-grown structure is lapped until the wafer is about 1/2 mm thick with the junction in the center. Contacts consisting of electroless nickel covered by electroplated rhodium are applied to both the p and n sides. The wafer is diced into square dice 1/2 to 1 mm on a side and the dice are etched sufficiently to remove approximately 1 mil of silicon. The following results are all for aluminum (p-side) and antimony (n-side) doped specimens with NA =3x 1018 per cm3, ND = 2-8 x 101A per cm3. The diodes are sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed and the capacitance remeasured. A special capacitance measurement method is used to insure a low sensitivity to shunt resistance. The diode is voltage driven and the current monitored by a phase lock amplifier. It is possible to adjust the detector phase to a point where shunt resistances as low as 100 O have no effect on the reading. The diodes in this study have a capacitance in the range 1000 to 5000 picofarads and a shunt resistance in the range 100 to l06 O depending on the stage of the anneal. THEORY The theoretical problem is twofold: 1) The computation of the amount of impurity diffusion and hence the impurity profile resulting from a given amount of vacancy motion, and 2) the computation of the capacitance from the impurity profile. A comparison of the theoretical and experimental capacitance (in particular the changes) yields the amount of vacancy motion. Vacancy Motion. A convenient parameter to measure the total amount of vacancy motion is Jv the total number of vacancy jumps per unit volume. Although this parameter varies with position in the crystal, owing to vacancy annihilation at the surfaces, it is approximately independent of position far from the surfaces, i.e. in the junction region. In terms of the number of vacancies per unit volume Nv and the vacancy diffusivity given by

Jan 1, 1970

By J. K. Stanley

Knowledge of the diffusivity of carbon in the low temperature form of iron (alpha iron existing below 910°C) is at the moment of considerable interest in the study of the decomposition of austenite and martensite, the elastic after-effect,123 the magnetic after-effect4 and the decarburization of steel below 910°C. Information on the solubility of carbon in iron, and to a lesser extent its diffusion, is also important in consideration of such phenomena as blue-brittleness, temper-brittleness, "magnetic" aging, quench-aging, strain-aging, and possibly the yield point. In order to obtain more information on these subjects more fundamental knowledge is necessary. It is the purpose of this work to present data on the diffusion and solubility of carbon in the alpha iron. The high temperature form of iron (gamma; face-centered cubic) existing above 910°C is capable of dissolving relatively large amounts of carbon, up to 1.7 pet at 1130°C, while the low temperature form (alpha, body-centered cubic) existing below 910° dissolves only a limited maximum amount of less than 0.02 pet carbon at 725°C, according to data obtained here. Since the solubility of carbon in the face-centered or gamma iron is large, relatively speaking, no great analytical difficulties have been encountered in the determination of the solubility lines5 or of the diffusion of carbon.0 The limited solubility of carbon in alpha iron offers difficulties because experimental procedures and analytical methods for low carbon contents below say 0.01 pet have to be more refined than techniques used for work with gamma iron. Because of the difficulties of applying conventional methods to the determination of the diffusion of carbon in alpha iron, virtually no work has been done on this subject. However, by proper refinement of the analytical method for small amounts of carbon, the determination of the diffusion coefficient can be made readily using modified procedures. The solubility of carbon in alpha iron has been determined over a temperature range by various investigators, but the agreement among them is poor. The present investigation establishes the limits quite accurately. Information of this kind is useful in establishing the correctness of equilibrium diagrams but, more significantly, such information on maximum solubilities, especially when extended to alloyed ferrites, should be extremely important in the study of aging and related phenomena. Literature The literature existing on the diffusion, in particular, and on the solubility of carbon in alpha iron is not extensive. The data which exist are not of a high order of accuracy, much of them being in the realm of conjecture. THE DIFFUSION OF CARBON IN ALPHA IRON Whiteley7 made the qualitative ob- servation, using metallographic techniques, that the rate of diffusion of carbon at the A1 (725°C) point was very rapid and that its diffusion was still rapid at 550°C. Snoek,4 studying the magnetic aftereffect in high purity iron, arrived at the conclusion that the after-effect could be explained by the presence of small amounts of carbon diffusing under the influence of magnetostrictive strain (lattice distortion due to magnetic interaction). In later work, Snoek8 made an estimate of the ratio of carbon diffusion in alpha to its diffusion in gamma iron, and concluded that for a temperature of 910°C the ratio of Da/D? was 2600. Polder,9 basing his calculations of D on relaxation phenomena in the elastic after-effect, estimated that Da is about 1/3 of D? at 910°C (1183°K) and is about 1/12 of Dy at 727°C (1000°K). Polder&apos;s equation for the diffusion of carbon in alpha iron was calculated to be 18000 D = 5.2 X 10-4 e-RT cm2 per sec Ham10 obtained data for the diffusion and solid solubility of carbon in alpha iron at two temperatures by using one technique similar to that employed in this study. He found a D of 8.0 X 10-7 cm2 per sec at 702°C and of 2.7 X 10-7 at 648°C. THE SOLUBILITY OF CARBON IN ALPHA IRON Although pearlite is absent in steels containing 0.06 pet,11 0.05 pet,12 or 0.045 pet C,13 it appears that the carbon in these steels cannot be in solution in ferrite. The solubility of carbon at the A1 (725°C) point was first determined by Scott14 on the basis of cooling curves, and was found to be between 0.03 and 0.04 pet C. Tamura15 by interpolating between the solubility of carbon in delta iron at 1400°C and in alpha at room temperature (assuming zero solubility) ar-

Jan 1, 1950

By Cyril Stanley Smith

BETA brass (consisting of approximately equal atomic proportions of copper and zinc) exists as a random solid solution at high temperatures, but at low temperatures [ ] an ordered structure is stable, with the copper and zinc atoms occupying alternate sites on the body-centered-cubic lattice. On cooling, ordering commences at a temperature of 450° to 490°C., depending on the composition. The degree of ordering progressively increases at lower temperatures until it becomes virtually complete at about 100°C. The electrical resistivity of the alloy illustrates the changes clearly (Fig. I). This type of reaction has been a favored subject for study by physicists. An [ ] excellent summary of the theory is to be found in a paper by F. C. Nix and W. Shockley.1 All published data on electrical conductivity, specific heat and other properties agree in indicating that the ordering reaction in beta brass takes place so rapidly that it cannot be prevented or even retarded by quenching. With most ordered alloys, cold-working induces disorder and

Jan 1, 1942

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."&apos; In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.&apos; A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above&apos; 1.1 indicate good coking tendencies. Although generally usable, this formula &apos;is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."&apos; In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.&apos; A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above&apos; 1.1 indicate good coking tendencies. Although generally usable, this formula &apos;is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953

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&apos; 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