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By M. E. V. Plummer, F. E. Beamish, J. C. Hole, J. M. Kavanagh

Prior researches have shown that the iron-copper-nickel content of platinum concentrates may be reduced by carbon to form a collecting alloy for the platinum metals in a manner exactly analogous to the formation of the lead fire assay button. The nature of the iron-copper-nickel alloys with the platinum metals has been investigated. Palladium and probably some of the other platinum metals form solid solutions with this alloy. ONE of the greatest known reserves of the platinum metals is to be found in the nickel, copper, iron sulphide deposits of Northern Ontario. The very large tonnage of copper-nickel ore processed makes the Sudbury district a significant world source of the platinum metals, the latter being recovered as byproducts in the electrolytic refining process for copper and nickel. Chalcopyrite, pentlandite, and pyrrhotite are carriers of the platinum metals;' these minerals contain from 0.03 to 2.0 ppm of the noble metals. The analysis of the above ores for the platinum metals necessitates an initial concentration of the minute quantities present in the ore. The method usually employed involves the extraction of the noble metals by molten lead with or without small proportions of silver. The lead is then separated from the precious metals by cupellation, a process which involves absorption by the cupel and volatilization of lead oxide, leaving the precious metals collected in a silver bead on the surface of the cupel. The collection by lead is probably achieved by a process of dissolution followed by some degree of segregation in the lead alloy since the cold button is seldom uniform in composition. With silver-lead alloys this process of liquation has been used to re- cover pure lead since, during the cooling period, crystals of pure lead separate and silver becomes concentrated toward the center of the solid.' Platinum and gold liquate in a manner similar to silver which may account for the successful recovery of platinum by fire assay even though it is considered insoluble in a solid lead medium. 3 In the case of iridium the liquation process may be a disadvantage in that the iridium may appear in the outer areas of the button and thus be lost mechanically during the handling processes. In any case the deficient alloying characteristics of lead for the platinum metals encouraged attempts to find an improved collecting alloy, and by analogy with aqueous extractions, preferably one in which solid solutions would be readily formed. Since, beyond a certain minimum solute to solvent ratio, the formation of a solid solution is accompanied by a lattice distortion, one would expect some relationship between the atomic diameters of any two metals and their tendency to form a solid solution. In one survey5 the hypothesis was put forward that when the atomic diameter of the solute differs by more than about 15 pct from the solvent, the "size factor" is unfavorable and the formation of a solid solution is restricted. On the other hand, when the atomic diameters are within this limit the size factor is favorable and solid solutions are readily formed, e.g. the transition metals of Group VIII having similar radii form solid solutions over wide ranges of composition.6 Even with a favorable size factor, elements having different crystal structures cannot form a continuous series of solid solutions. Cell dimensions alter as the concentration of the solute increases, causing a

Jan 1, 1962

By Herbert Dumont

Since 1947 Preussag AG Metal1 has used a process for fuming zinc- and lead-containing dump slags and residues from vertical retorts in a half-shaft furnace at their Hüttenwerk Harz at Oker. Contrary to the classic shaft furnace, only one side of the half-shaft furnace is fitted with tuyeres. The opposite side is a bricked slope. The upper shaft section is piped. There zinc vapor and combustion gases are burned by sucked-in air. Gases and fume enter a boiler located on the rear length of the furnace via a piped fire bridge. The gases are then cooled in an air preheater prior to dedusting in a bag filter. The furnace is charged with briquettes of metal-bearing materials, coal and pitch. The leaded zinc oxide fume is comparatively rich in both lead and zinc. The copper in the feed is recovered in low-copper matte. The slag can be discarded. The Oker plant comprises 13 furnaces of 2.9 to 4.9 m length in the tuyere area. Two other plants in Italy and Spain are processing zinc leach residues by this technique. Fuming of zinc-lead-oxide ores as well as partially roasted sulfide- zinc-lead-copper bulk concentrates will be possible.

Jan 1, 1970

By Wm. R. Webster

This is a contribution for the proposed new discussion on the physics of steel. The former discussion on the subject started with the consideration of five papers presented at the Chicago meeting in 1893, and continued for several years. The Suggested Lines of Discussion, prepared by Doctor Howe, covered a wide field and added greatly to the success of the work. Naturally, the first step in a new discussion will be to remodel and bring up to date the old Suggested Lines of Discussion so as to embody all the important advances in the metallurgy of steel that have a bearing on the physics of steel and keep the papers and discussions within the field of work undertaken. This paper will be devoted to the practical application, in rolling steel, of the effects of carbon, phosphorus, and manganese on its tensile strength, with some suggestions on further research work. Dr. J. E. Stead, in his paper Influence of Some Elements on the Mechanical Properties of Steel,' gave a complete review of all that had been done during the past thirty years. He gave full credit to all investigators who worked on these lines, also their results, with his views on same, and in many cases his own results. All of this data and much new valuable information were put in convenient shape for reference and study. To do this required a great deal of work, which is fully appreciated by the steel manufacturers and investigators. The variations in the values given by the different investigators for the increase of the tensile strength of steel for each 0.01 per cent. of carbon, phosphorus, and manganese were largely due to the steels they worked on, the large or small variations in the amount of the elcments present, and the omission to take into consideration all the factors, from the blast furnace through to finished rolled material, that affect the character of the steel. For instance, a poorly made dirty steel requires considerably more carbon to give the same ultimate strength than a well-made clean steel with the same phosphorus and manganese content.

Jan 1, 1922

By Wm. R. Webster

This is a contribution for the proposed new discussion on the physics of steel. The former discussion on the subject started with the consideration of five papers presented at the Chicago meeting in 1893, and continued for several years. The Suggested Lines of Discussion, prepared by Doctor Howe, covered a wide field and added greatly to the success of the work. Naturally, the first step in a new discussion will be to remodel and bring up to date the old Suggested Lines of Discussion so as to embody all the important advances in the metallurgy of steel that have a bearing on the physics of steel and keep the papers and discussions within the field of work undertaken. This paper will be devoted to the practical application, in rolling steel, of the effects of carbon, phosphorus, and manganese on its tensile strength, with some suggestions on further research work. Dr. J. E. Stead, in his paper Influence of Some Elements on the Mechanical Properties of Steel,' gave a complete review of all that had been done during the past thirty years. He gave full credit to all investigators who worked on these lines, also their results, with his views on same, and in many cases his own results. All of this data and much new valuable information were put in convenient shape for reference and study. To do this required a great deal of work, which is fully appreciated by the steel manufacturers and investigators. The variations in the values given by the different investigators for the increase of the tensile strength of steel for each 0.01 per cent. of carbon, phosphorus, and manganese were largely due to the steels they worked on, the large or small variations in the amount of the elcments present, and the omission to take into consideration all the factors, from the blast furnace through to finished rolled material, that affect the character of the steel. For instance, a poorly made dirty steel requires considerably more carbon to give the same ultimate strength than a well-made clean steel with the same phosphorus and manganese content.

Jan 1, 1922

By Arnulf Muan, Klaus Schwerdtfeger

Equilibrium ratios C02/C0 of a gas phase coexisting with selected phase assemblages of the system Fe-Mn-0 have been determined in the temperature range 1000" to 1300°C. The oxygen pressure for the "hfnO" +hfn30, equilibrium and for the "(Fe,hTn)O" + (Fe,Mnh 0* equilibrium at high manganese contents has been determined by electromotive force measurements using stabilized zirconia as a solid electrolyte. The notstoichometry 01' "hTnO" and of "(Fe, iM1z)O" solid solutions has been determined by ther-mog-/avi?netry and by wet-chemical analysis. The data obtained are used to derive activity-composition relations in "(Fe,hfn)O" and (Fe,Mn),O4 solid solutions. WUSTITE "FeO" and manganosite "MnO" form a continuous series of solid solution at high temperatures,' and so do magnetite Fe304 and the high-temperature, cubic modification of Mn304 (Ref. 2) (high hausmannite, -1170). The oxides "FeO" and "MnO" are cation-deficient phases.495 The nonstoi-chiometry of "(Fe,Mn)O" solid solutions has been studied by Engell and ~ohl' at two selected C02/C0 ratios at 1250°C. The two oxide end members of the spinel solid solution, FesO4 and Mn,04, however, are known to be close to stoichiometric under the experimental conditions used in the present investigation.''' The oxygen pressures of "(Fe,Mn)07' solid solutions in equilibrium with iron have been determined by Schenck and coworkers,8 by Foster and welch," and by ~n~e1l.l' The two former groups equilibrated the condensed phases in C02-CO atmospheres of lmown compositions, whereas Engell" used a galvanic cell with stabilized zirconia as a solid electrolyte. The results of these investigators are not in good agreement. Activities of FeO in manganowiistite as calculated from the results of Foster and Welch show ideal behavior, those of Engell yield a pronounced positive deviation, and those of Schenck et 01. show a moderate positive deviation from ideality. In the present work oxygen pressures for the iron + manganowiistite and manganowustite + spinel equilibria and the nonstoichiometry of manganowiistites have been measured. The data were used to calculate activities in the manganowiistite and spinel solid solutions. EXPERIMENTAL METHODS The COz/CO ratios at which manganowustite and iron are in equilibrium were determined by thermo-gravimetric and quenching methods. Experimental details are described in a previous publication.'2 In the thermogravimetric technique, incipient reduction of manganowiistite pellets to metallic iron was observed as a break in the weight vs log COZ/CO curve. In the quenching technique, manganowiistite samples were partially reduced to metallic iron, or the metallic iron of manganowustite + metallic iron mixtures was partially oxidized to manganowustite, in atmospheres of constant C02/CO ratios. After quenching the composition of the oxide phase was determined by X-ray lattice parameter measurements and comparison with a standard curve obtained from oxide solid solutions of known compositions. The nonstoichiometry of "MnO" and "(Fe,Mn)07' solid solutions was determined by chemical analysis of samples equilibrated in C02-CO atmospheres and quenched to room temperature, as well as thermo-gravimetrically by reducing (Fe,Mn),04 or Mn304 to manganowiistite or manganosite. The equilibrium between manganowiistite and (Fe,Mn),04 was measured thermogravimetrically by reducing (Fe,Mn),04 solid solutions having composition in the range of %„ l(NFe +NM) from 0 to 0.63. No experiments could be performed with this technique at higher manganese contents, because the equilibrium C02/C0 ratios are too large for accurate control. An additional difficulty arises at the higher manganese contents due to the strong increase in oxygen content of the manganowustite phase with increasing log Py near the manganowiistite-spinel boundary. Consequently a sharp break in the weight loss vs log C02/CO curve cannot be observed at the phase boundary. At high manganese contents of the manganowiistite, e.g., (NMn/(NF~ + NMn) > 0.9, electromotive force measurements with stabilized zirconia as a solid electrolyte were made to determine the equilibrium oxygen partial pressure. Experimental details are described in a previous paper.* Mixtures of "(Fe,Mn)O" and (Fe,Mn),04 were pressed to pellets, and the oxygen pressure of the equilibrated samples was compared to that of Ni + NiO mixtures in the cell The composition of the manganowiistite in the equilibrated two-phase mixture was determined by lattice parameter measurements and comparison with known standards. The oxygen pressure for the Ni + NiO equilibrium was taken from available data.l3~l4 No reliable results were obtained with the electromotive force technique on iron-rich oxides. The electromotive force drifted strongly with time in this composition range. An additional difficulty arises from the partial de-

Jan 1, 1968

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach's work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,' who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750'F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968

By C. S. Westerberg, C. P. Heiner

Observation of the clinkering action of coal from the Castle Gate D seam in underfeed stokers over a period of years has given rise to the present investigation of the effect of bony coal on clinkering. Some very costly examples of slagging clinkers in particular cases have been of especial interest to the authors. In such cases coal analyses and ash-softening and fluid temperatures have been found of little value. In general, it was noted that slagging mas accompanied by a somewhat higher ash content of the stoker slack, and the suspicion naturally arose that foreign matter was the troublemaker. One would naturally suspect bony coal and rock impurities because of their occurrence and prevalence within the seam and the relative absence of sulphur or other impurities in the coal mined. The test results given herein indicate that the concentration of the bony coal and rock impurities in the coal determines the clinkering tendencies of the ash during combustion. Castle Gate D Seam Extending from the Utah-Colorado line near Grand Junction, Colo., westward to Greenriver, Utah, and thence in semicircular form north and westward to Castle Gate, and from there southward to Mt. Hilgard in central Utah, is a line of nearly perpendicular cliffs, composed of interbedded massive sandstone and shales, making up the coal-bearing horizon of the Mesaverde formation of Upper Cretaceous age. The cliffs face roughly concentrically toward the south and southeast and the strata, with conformably enclosed coal beds, gently dip away from the face of the cliffs and at right angles to their front line. Back of these cliffs the mountain masses rise to an altitude of from 8000 to 10,ooo ft. above sea level. Stretching away from their foot is a great shale plain, on which the towns are situated and over which the railroad lines and highways run. The Castle Gate mines enter the coal beds at their outcrop; the workings extending within a particular coal bed away from the outcrop and under the mountain mass back from the cliff line (Fig. I). Throughout the Mesaverde formation in the Castle Gate general area, there are from two to five workable coal beds. Usually not all of these are coincidentally of workable size and merchantable quality throughout any given large tract. In the Castle Gate mine area, the base of the Mesaverde horizon and coal measures is marked by a massive, cliffmaking, gray sandstone bed 60 to 80 ft. thick. Locally this is referred to as the "Castle Gate sandstone floor." Frank R. Clark, in U. S. Geol. Survey Bull. 793, designates it as the "Aberdeen sandstone." At Castle Gate the various coal beds are designated by the letters A, B, C, etc., commencing with the lowest bed.

Jan 1, 1942

By C. P. Heiner, C. S. Westerberg

Observation of the clinkering action of coal from the Castle Gate D seam in underfeed stokers over a period of years has given rise to the present investigation of the effect of bony coal on clinkering. Some very costly examples of slagging clinkers in particular cases have been of especial interest to the authors. In such cases coal analyses and ash-softening and fluid temperatures have been found of little value. In general, it was noted that slagging mas accompanied by a somewhat higher ash content of the stoker slack, and the suspicion naturally arose that foreign matter was the troublemaker. One would naturally suspect bony coal and rock impurities because of their occurrence and prevalence within the seam and the relative absence of sulphur or other impurities in the coal mined. The test results given herein indicate that the concentration of the bony coal and rock impurities in the coal determines the clinkering tendencies of the ash during combustion. Castle Gate D Seam Extending from the Utah-Colorado line near Grand Junction, Colo., westward to Greenriver, Utah, and thence in semicircular form north and westward to Castle Gate, and from there southward to Mt. Hilgard in central Utah, is a line of nearly perpendicular cliffs, composed of interbedded massive sandstone and shales, making up the coal-bearing horizon of the Mesaverde formation of Upper Cretaceous age. The cliffs face roughly concentrically toward the south and southeast and the strata, with conformably enclosed coal beds, gently dip away from the face of the cliffs and at right angles to their front line. Back of these cliffs the mountain masses rise to an altitude of from 8000 to 10,ooo ft. above sea level. Stretching away from their foot is a great shale plain, on which the towns are situated and over which the railroad lines and highways run. The Castle Gate mines enter the coal beds at their outcrop; the workings extending within a particular coal bed away from the outcrop and under the mountain mass back from the cliff line (Fig. I). Throughout the Mesaverde formation in the Castle Gate general area, there are from two to five workable coal beds. Usually not all of these are coincidentally of workable size and merchantable quality throughout any given large tract. In the Castle Gate mine area, the base of the Mesaverde horizon and coal measures is marked by a massive, cliffmaking, gray sandstone bed 60 to 80 ft. thick. Locally this is referred to as the "Castle Gate sandstone floor." Frank R. Clark, in U. S. Geol. Survey Bull. 793, designates it as the "Aberdeen sandstone." At Castle Gate the various coal beds are designated by the letters A, B, C, etc., commencing with the lowest bed.

Jan 1, 1942

By R. J. Marcotte, C. T. Eddy, R. J. Smith

The objectives of the investigation herein reported were to determine: (I) the S-curves for certain selected cast steels, (2) whether or not the published S-curves for wrought steels are satisfactory for use on cast steels of similar composition, and (3) to prepare hardenability curves of the selected cast steels. In order to make the final comparisons between cast and wrought steel more completely tangible, it was deemed advisable not only to determine S-curves for the steels submitted in the cast condition but also to roll some of the cast-steel test bars and determine comparison S-curves on such wrought material. This procedure eliminates the composition variable and makes it possible to reveal the differences resulting from plastic deformation of the cast structure in addition to providing the comparison with published data on wrought steels. Cast Steels The cast steels selected for the preparation of S-curves, or time-temperature transformation curves, were similar to S.A.E. series 1030, 2330, 4130 and 4330. Of these the 1030 was supplied by The Crucible Steel Casting Co., Cleveland, Ohio, and the other three by The Sawbrook Steel Castings Co., Lockland, Ohio. The steels were furnished in the as-cast condition. The manufacturers supplied the chemical analyses and the properties that could be obtained in the heat-treated condition—all of which is summarized in Table I. The metallographic and dilatometric procedures and equipment were in general standard. The specific technique employed was described in a report of the Steel

Jan 1, 1945

By J. O. Brittain, E. P. Lautenschlager, F. Felberbauer

This investigation was undertaken to evaluate the effect of a dispersed phase in a iron upon the strain hardening and the stress dependency of dislocation velocity as inferred from the strain-rate sensitivitv. Experiments were made in a-iron specimens with controlled amounts of carbon and/or A12O3. They were tested at various temperatures between 195' and 373 'K under a variety of conditions oj-concentration, strain rate, and quench aging. The resulting yield strength, flow strength, and strain hardening increased with addition of Al2O3. The parameter m, measured from changes in strain rate, was xsed to describe the stress dependency of the dislocation velocity. m was found to increase with additions of A12O3, increasing carbon in solution, and with increasing temperature. When applied to a recent model for yielding based upon dislocation multiplication and velocity characteristics, the values of m alone did not successfully predict yielding for the materials of this investigalion, but had to be adjusted with a consideration of the number of unlocked dislocations nucleated heterogeneously at discontinuities or inclusions. The change of yield strength with Al2O3 Interpar-ticle spacing appeared to obey a theory of Orowan. EVER since the concept of dislocations has been introduced to explain plastic deformation in crystalline materials, the origin of dislocations and the source of the number of dislocations required to account for plastic deformation have been persistent questions. Ruling out the possibility of homogeneous nucleation,' Gilman2 drew attention to the various cases of heterogeneous nucleation as the source of dislocations, whereas Frank and Read3 introduced the Frank-Read source. However, Gil-man found that the Frank-Read sources did not play a dominant role in the deformation of LiF crystals, but that small precipitates are often, if not always, associated with the nucleation of dislocations. In LiF crystals, however, most of the dislocations arose through the multiplication of moving dislocations in a mechanism described by Koehler4 and Orowan,5 Thus, relatively few precipitates could account for a large number of dislocations. A similar observation of dislocation nucleation at inclusions of precipitates was made by Stein and LOW' on Si-Fe crystals. Their crystals contained

Jan 1, 1964

By W. L. Eaton, S. H. Ash

A barrier pillar in the anthracite region of Pennsylvania is a portion of the bed that is left unmined along the property line or lines of adjoining mining properties, or between mines, or between parts of mines. Barrier pillars perform important functions in anthracite-mining operations. Their principal function is to act as dams to prevent water that accumulates in a mine from suddenly breaking into an adjacent mine or into adjacent mine workings and causing loss of life, property, or both. More than 83 billion gal of water is impounded in II; underground water pools in anthracite mines.1,2 These pools are confined by a system of barrier pillars which separate adjacent mines. The principal factor that threatens to cut short the life of the anthracite industry, to curtail production, and to affect the economic structure of the people and business dependent on anthracite for their livelihood is the inundation of anthracite mines.l,2,4,13,29 To obtain a clear picture of the anthracite mine-water problem, it is necessary to understand the part played by the barrier pillars that separate adjoining mines. Purpose of Report The purpose of this report is to show the methods of determining the size of barrier pillars in the anthracite region, to present the hazards that exist because of the lack of sound engineering being applied to the size of many existent barrier pillars, and to suggest a method whereby barrier pillars can perform the function for which they are intended. The Barrier-pillar Problem Article 111, section '10, of the Anthracite Mining Laws of Pennsylvania reads thus: It shall be obligatory on the owners of adjoining coal properties to leave, or cause to be left, a pillar of coal in each seam or vein of coal worked by them, along the line of adjoining property, of such width that, taken in connection with the pillar to be left by the adjoining property owner, will be a sufficient barrier for the safety of the employees of either mine in case the other should be abandoned and allowed to fill with water; such width of pillar to be determined by the engineers of the adjoining property owners together with the inspector of the district in which the mine is situated, and the surveys of the face of the workings along such pillar shall be made in duplicate and must practically agree. A copy of such duplicate surveys, certified to, must be filed with the owners of the adjoining properties and with the inspector of the district in which the mine or property is situated. Mining practices with regard to barrier pillars have varied greatly since mining began. In many anthracite mines the barrier pillars have been weakened or punctured. As a consequence, the condition

Jan 1, 1949

By E. C. van Reuth

FIFTY-three alloys have been examined in the Fe-W and Co-W alloy systems in an attempt to verify the finding of o phases in these systems as reported by Goldschmidt.' The alloys were examined metallographically and by X-ray diffraction. The 10-g specimens were made by powder metallurgy techniques. Very fine, high-purity powders were compressed in a double-acting die at 120,000 psi after hydrogen reduction. All compacts were then sintered for 200 hr at 950°C in a helium atmosphere. Metallographic investigation and X-ray diffraction proved this time to be sufficient to allow complete homogenization before the subsequent high-temperature anneal. Each specimen was then sealed into an evacuated silica capsule and annealed at 1400"or 1500 C (except two) for 25 hr. (The 60 pct Fe and 55 pct Co alloys taken to 1610"and 1680°C respectively were held at these temperatures for 1hr. However, since these structures were at equilibrium before the anneal, and in view of their resultant structures, it is assumed that they reached equilib-

Jan 1, 1960

By Willard S. Morse

In my paper on "The Lixiviation of Silver-Ores by the Russell Process at Aspen, Colorado" (page 137 of the present volume), attention was called to the decrease in "chlorination " during the washing of the roasted ore with water, to remove soluble salts, before leaching with hyposulphite and Russell solutions. This decrease in " chlorination," which is due to conversion of the silver chloride to some other form not soluble in hyposulphite solutions, and which, for the sake of brevity, will be termed the "going-back" of chlorination, has been a serious obstacle to the successful operation of several leaching-works, and was at Aspen the only difficulty encountered. I have never seen any explanation of the cause of this failure to extract, in actual practice in the mill, the amount of silver chloride shown by laboratory-leachings to be present in the roasted ore; and the purpose of this paper is to record the conclusions arrived at concerning the cause of the phenomenon, and the data upon which they are based. The average decrease in chlorination by washing with water in the Aspen ores for a period of fourteen months was as follows:

Jan 1, 1896

By Howard A. Meyerhoff, J. Earl Frazier

It is not known when silica sand was first noticed along the north coast of Puerto Rico, but the first mention of its occurrence was made in 1922, by N. L. Britton,1 who described its presence in isolated patches extending from Loiza westward beyond Manati. Further observations were made in 1925 and 1926 by Meyerhoff,2 who extended the known occurrences still farther westward to the low hill belt in the Quebradillas limestone immediately south of Hatillo. The extraordinary purity of the sands, which in most localities exhibit no contamination from the non-siliceous materials surrounding them, was quickly appreciated, and the feasibility of utilizing them for the manufacture of glass was investigated, initially by the Committee on Mineral Resources3 and later (1936) by the Puerto Rico Recon-structionAdministration and by H. C. Ray, mining engineer of the Insular Bureau of Mines. In 1934 samples submitted to the Hazel Atlas Glass Co., of Washington, Pennsylvania, were reported to have the composition as shown in the table on column two. Appreciation of the quality of the sand prompted geological and quantitative studies of the deposits, as well as cornmercial investigations to determine the feasibility of utilizing it locally or on the mainland for the manufacture of glass containers. Distribution of the Sands The quartz sands consistently lie within the outcrop area of the Quebradillas limestone, the youngest of the Miocene formations in the Tertiary coastal plain that fringes the northern coast of the Island. Many of the deposits are closely associated with limestone outcrops, but some appear to be embedded in lagoonal sediments at some distance from rock exposures, and at least one deposit, near Dorado, has been reworked by waves and littoral currents. With this single known exception, the deposits consist of irregular, patternless patches of white sand, which have sharply defined contacts with the surrounding material. Although patches of sand are present in a 90-km. belt that is not more than 5 km. wide, extending from Loiza to Hatillo, they attain maximum size, purity and number in the north central coastal area between Dorado and Barceloneta. Fifty separate deposits have been mapped in Lago Tortuguero and to the south of it, some as small as 50 ft. in diameter but

Jan 1, 1948

By J. Earl Frazier, Howard A. Meyerhoff

It is not known when silica sand was first noticed along the north coast of Puerto Rico, but the first mention of its occurrence was made in 1922, by N. L. Britton,1 who described its presence in isolated patches extending from Loiza westward beyond Manati. Further observations were made in 1925 and 1926 by Meyerhoff,2 who extended the known occurrences still farther westward to the low hill belt in the Quebradillas limestone immediately south of Hatillo. The extraordinary purity of the sands, which in most localities exhibit no contamination from the non-siliceous materials surrounding them, was quickly appreciated, and the feasibility of utilizing them for the manufacture of glass was investigated, initially by the Committee on Mineral Resources3 and later (1936) by the Puerto Rico Recon-structionAdministration and by H. C. Ray, mining engineer of the Insular Bureau of Mines. In 1934 samples submitted to the Hazel Atlas Glass Co., of Washington, Pennsylvania, were reported to have the composition as shown in the table on column two. Appreciation of the quality of the sand prompted geological and quantitative studies of the deposits, as well as cornmercial investigations to determine the feasibility of utilizing it locally or on the mainland for the manufacture of glass containers. Distribution of the Sands The quartz sands consistently lie within the outcrop area of the Quebradillas limestone, the youngest of the Miocene formations in the Tertiary coastal plain that fringes the northern coast of the Island. Many of the deposits are closely associated with limestone outcrops, but some appear to be embedded in lagoonal sediments at some distance from rock exposures, and at least one deposit, near Dorado, has been reworked by waves and littoral currents. With this single known exception, the deposits consist of irregular, patternless patches of white sand, which have sharply defined contacts with the surrounding material. Although patches of sand are present in a 90-km. belt that is not more than 5 km. wide, extending from Loiza to Hatillo, they attain maximum size, purity and number in the north central coastal area between Dorado and Barceloneta. Fifty separate deposits have been mapped in Lago Tortuguero and to the south of it, some as small as 50 ft. in diameter but

Jan 1, 1948

By S. S. Clarke

Late in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of Jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of Jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1949

By L. E. Murr, P. J. Smith

A study has been made by transmission electron microscopy of thin foils of 304 stainless steel fatigued external to the electron microscope in reversed bending, and of thin foils fatigued directly within the microscope in alternating tension. The build-up of stacking faults in the thin foils during fatigue zoas correlated with the dislocatirm structures found in thin films prepared fror fatigued bulk specimens. The performance of the special devices designed for fatigue of thin foils so outlined and the importance of alternative methods of preparation of more uniform fatigue specimens bY vapor deposition are emphasized. INVESTIGATIONS on fatigued bulk aluminum1,' and stainless stee13j4 have revealed the existence of dislocation substructure on examination by transmission electron microscopy of electrolytically thinned foils representative of these bulk specimens. While this technique has proved extremely valuable, it has several shortcomings. First, the method of fatiguing bulk specimens and then thinning to foil for electron-transmission observation allows only one observation of internal structure at any one portion of the fatigue life. Second, thinning the bulk fatigued specimens to foil results in the loss of at least one original surface. Thus, what one sees in the remaining electron-transparent sections is an internal dislocation or fault structure which in many cases cannot be correlated with the original surface markings. This is an undesirable feature, since it is well-known that metal surfaces play an important part in the fatigue process.5 An obvious third undesirable feature of the thinning-from-bulk technique is the fact that static observations have difficulty (in the case of fatigue) explaining the mechanism of a dynamic process. What is required then is a method whereby a selected thin area can be continuously observed either while undergoing cyclic deformation or at various fixed stages of fatigue deformation. While Murr and wilkov6 have reported some success with an apparatus designed to fatigue thin metal foils directly within the electron microscope, the nature of the specimen-mounting procedure and the mechanical features involved in the adaptation of the fatigue device to the electron microscope make this method difficult to operate. It was not possible, for example, to make frequent observations of a selected area because of difficulty in maintaining a chosen area in a stable viewing position inside the electron microscope. Except for the build-up of a dislocation substructure and what are commonly referred to as "slip striations", little else has been reported from observations on thin-foil sections prepared from bulk fatigue specimens. segal17 has found "slip striations" in stainless-steel fatigued specimens which were electropolished from both sides, but gave no explanation as to their origin or identity in terms of lattice imperfections. The research to be reported in this paper was undertaken with the following objectives in mind. First, an attempt was made to devise a technique or techniques whereby thin metal foils could be fatigued and repeatedly observed by transmission electron microscopy. Second, it was hoped that some correlation could be made between deformation striations found in fatigued thin transmission specimens and thin foils prepared from bulk fatigued specimens. These investigations illustrate quite convincingly that a feasible method is available for the direct study of the fatigue mechanism and similar dynamic phenomena in thin transmission specimens inside the electron microscope. I) EXPERIMENTAL METHODS Three modes of specimen fatigue and observation of fatigue damage were used. These involved fatigue of thin-foil specimens in a special arrangement external to the electron microscope and observation of a selected area at various stages in the fatigue life, the fatigue of thin-foil transmission specimens inside the electron microscope, and the fatigue of bulk specimens external to the electron microscope followed by thin-foil preparation for direct observation at predetermined stages. Design of the External Fatigue Clip and Specimen Holder for the Hitachi H.U.11 Electron Micro-scope. The purpose of the fatigue clip was to provide a reversed bending fatigue stress to a thin-foil transmission specimen outside the electron microscope. In order to accomplish this, a flat-bottomed, U-shaped brass clip was made as shown

Jan 1, 1965

By Charles L. Thomas

A novel, highly sensitive, and reproducible nzetlzod for the determination of hydrogen in solid materials is presented. The procedure requires equilibration of the specimen with hydrogen gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subse-quent quantitative analysis by mass spectroscopy. Good linearity is obtained for the Arrl~enius plots of the investigated metals. The advantages in the use of this method over that of Sieverts aye discussed. The solubility data for copper are in reasonable agveewzent with a considerable number of other inuestigations, wllile those fov silver are considerably lower than previously reported. The first known solubility data for gold are presented. Solubility equations and heats of MUCH of the data which are available on the solubility of hydrogen in various metals and alloys have been obtained by the classical Sieverts method.' The method involves the measurement of a decrease in pressure of a gas in a calibrated system, and the calculated contraction in volume is attributed to the solubility of the gas in the metal sample. The procedure requires several corrections, such as the solubility of the gas in the container walls and the diffusion of the gas through these walls, as noted by Steacie and .Johnson2 and others. In addition, errors may be incurred due to reactions between metal surface impurities, such as oxides, and the saturating gas. The precise calibration of the measuring system where large thermal gradients exist can present additional difficulties. Also, accurate volumetric measurements of small quantities of gas are difficult. Many of the objections to the Sieverts method were overcome on solid materials by Ransley and ~eufeld,~ who first saturated the metal with hydrogen and performed a subsequent extraction and measurement of the gas by chemical means. Eichenauer and pebler4 and Eichenauer, Kiinzig, and pebler5 measured the diffusion coefficient and solubility by following the degasification of a sample as a function of a rate of increase in pressure in a previously evacuated system. Here again, however, the procedure involves many of the corrections of the Sie-verts method. The present investigation deals with the solubility of hydrogen in solid copper, silver, and gold by a technique which eliminates many of the aforementioned corrections and possible errors. This procedure requires equilibration of the specimen with gas, rapid quenching, and hot vacuum extraction of the dissolved gas with subsequent quantitative analysis by mass spectroscopy. EXPERIMENTAL Two completely separate systems were employed to accomplish first, the equilibrium saturation of the sample and second, the extraction of the dissolved gas. Saturation Apparatus. The saturation apparatus, illustrated in Fig. l, consisted of a vertically mounted quartz tube with a three-way valve for vacuum or hydrogen near the top and an outlet near the bottom leading to a butyl phthalate seal. The bottom end of the tube was terminated with a joint accommodating an O-ring sealed "Asco Stirring Gland" (The Emil Greiner Co.). This gland facilitated movement of the thermocouple without introduction of air into the system. The upper portion of the tube (above the furnace) was water-jacketed. A Welsh 1405-B mechanical pump provided the necessary system evacu-

Jan 1, 1968

By Pol Duwez

The effect of the rate of cooling on titanium, zirconium, and thallium has been measured. For titanium-molybdenum alloys, it has been shown that for molybdenum concentration up to 8 pct the rate of cooling has no effect on the transformation temperature, but this temperature decreases progressively with increasing molybdenum content. HIGH strength to weight ratio and remarkable corrosion resistance have often been advanced as the main reasons for the present widespread interest in titanium. For the physical metallurgist, the existence of an allotropic transformation in titanium is another important factor. As in the case of iron, an allotropic transformation may be the fundamental property upon which the response of Ti-base alloys to heat treatment will depend. It is therefore important to study the mechanism of the allotropic transformation in pure titanium and the effect of alloying elements on this transformation. The existence of an allotropic transformation in titanium was reported in 1931 by Schulze.' Later, De Boer et al.' determined the transformation temperature from a discontinuity in the electrical resistivity at 882"42O°C. According to recent work," the transformation temperature is 882.5"&1°C. The crystal structure of the room temperature a phase is hexagonal close-packed and the high temperature fi phase is body-centered cubic.' It is well known that the high temperature /3 phase of pure titanium cannot be retained by quenching to room temperature. Several investigators'-' have shown that in alloys of titanium with metals which are soluble in the @ phase (for example, nickel, molybdenum, chromium, or manganese), the /3 structure can be retained, providing the concentration of the alloying element is greater than a certain critical value. Below this critical value, the alloys transform during quenching, at least partially, into a supersaturated solid solution having the a. structure. This behavior is very similar to that found in some iron binary alloys (Fe-Ni and Fe-Mh, for example) and is an indication that the transformation might occur by means of a shear mechanism analogous to that observed in the austenite-martensite reaction. The present investigation is mostly concerned with the effect of the rate of cooling on the /3 to a transformation. In the first portion of this paper, the results obtained on pure titanium are described. Two other pure metals, zirconium and thallium, were also investigated, because they both have an allotropic transformation like titanium, from an hexagonal close-packed to a body-centered cubic structure. For purposes of comparison, the effect of rate of cooling of the y to a transformation of iron was included in the experimental program. The second part of this paper deals with Ti-Mo alloys. The equilibrium phase boundaries involving the solid state reactions on the Ti-rich side of the system were determined and a study was made of the effect of the rate of cooling on the transformation of the high temperature /3 solid solution. Experimental Procedure Since the main object of the present investigation was the determination of the effect of the rate of cooling on a transformation temperature, the best technique available was that used by Greninger" in his study of the martensite arrest in carbon steels. This method consists of heating a very small sample of metal to which fine thermocouple wires are .attached, cooling the sample rapidly by means of a blast of helium, and recording the temperature vs. time curve on an oscillograph. The apparatus used in the present experiments was very similar to that described by Greninger, except that the heating coil was made of molybdenum wire (0.040 in. in diam) and the assembly was placed in a bell jar under vacuum of 10" mm Hg or less. The specimen con-

Jan 1, 1952

By S. F. Urban, G. Derge

At the time this investigation was initiated variations were observed in the quality of different heats of basic electric-furnace steels, although they had been made under purportedly similar conditions. This indicated that these variations were related to normally unobserved variations in the character of the bath, especially during the "refining" period. Although the slags used for this operation are commonly referred to as "reducing" slags, and are regarded as having a "deoxidizing" action on the bath, no reliable measurements of this action were available. It was decided, therefore, to study the behavior of oxygen in the metal for ' large enough number of heats to learn its normal variations and to relate these variations to regularly observed conditions of operation. The most important general conclusion reached was that the time a heat is held under a reducing 'lag should be reduced to a minimum, which was about an hour and a half under the conditions studied. Beyond this time no observable beneficial effects are obtained from the reducing slags, insofar as oxygen and sulphur content of the bath are concerned. It is likely that added time may increase hydrogen content as well as heat costs. The oxygen content of the bath is never reduced below the amount in equilibrium with the carbon. Concurrently with this work, J. S. Marsh1 presented data that supplement and support many of the results of this paper. Procedure The work was done in two different electric-furnace shops of the same plant. The selection of heats was made primarily with regard to the convenience of heat schedules. companion slag and metal samples were taken just prior to slag-ofi and throughout the refining period for an initial set of 17 heats, and before slag-off and near tap for an additional I3 heats. slag Sampling presented no particular problem; a spoonful of slag was poured onto a metal plate and when sufficiently cool was sealed in an airtight container. Sampling the metal for oxygen presented a more complex problem. Because of the lack of previous experience in sampling electric-furnace baths, a number of methods were compared. Chilled Wedge Samples2 An unkilled metal sample is removed from the furnace in a well-slagged car-bometer spoon and poured immediately into a heavy copper mold designed to provide rapid freezing. Three different types of molds were used to determine the optimum for electric-furnace hats. The Big wedge Mold (a) was a 4 by 4 by 4-in. split copper mold, yielding a wedge-shaped casting I in. wide, 1 1/2 in. long, and 34 in. maximum thickness, and was finally adopted as the most satisfactory design.

Jan 1, 1948