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By J. E. Hilliard

A procedure is described for determining, from measurements on a section, the moments of any degree n (i.e., the mean value of Dn, where D is a linear dimension) of the size distribution of particles (or grains) in an opaque sarnple. The analysis is applicable to particles of alnzost any shape and to any mixture of shapes. However, if absolute values of the wloments are required, it is necessary to know what shapes are present and the relative frequency of their occurrence. In addition, certain shape-dependent parameters have to be evaluated before the formulas can be used. The measurement required is the distribution of intercept lengths. This can be determined either visually or with an automatic scanning instrument. Corrections me derived for the bias due to instrumental end effects. The proposed analysis has the following advantages over existing ones: 1) Confidence limits are easily estimated for the measured properties or, conversely, the number of counts required to achieve a given accuracy can be determined. 2) The analysis is not restricted to particles of a special shape. 3) The error resulting from any known degree of departure of the actual from the assumed particle shape can be estimated. 4) The computations are simple and, apart from a change in constants, are independent of particle shape. 5) The number of particles per unit volume can be determined by a simple counting procedure. MANY procedures have been described for determining the size distribution of particles from measurements on a section (or plane of polish). They differ from one another in the property measured on the section (radius, intercept length, profile area) and in the method used for the numerical solution of the integral equation relating the property to the particle size distribution. However, all existing analyses share at least two of the following disadvantages. 1) They are limited to a particular shape of particle (usually spherical). 2) It is very difficult to determine how the statistical sampling error is propagated into the computed size distribution. The investigator thus has no means of knowing the reliability of his result and, what is of equal concern, he is unable to estimate how many measurements are required to obtain a result of the required accuracy. 3) It is also difficult to assess the error resulting from any deviation between the actual and assumed particle shape. The foregoing limitations stem from the complex relationship between the particle size distribution and the distribution of the property measured on the section. As will be shown, they can be avoided by defining the size distribution in terms of discrete parameters

Jan 1, 1969

By R. M. Douthwaite, G. Birkbeck

The effect of grain size and specimen dimensions on the occurrence and magnitude of a yield point drop in pure iron has been examined. The tests were done at room temperature. The results indicate that gain size is the critical factor determining whether a yield drop occurs. The specimen diameter:gain size ratio does not influence the magnitude of the yield drop for the range of gain size and specimen diameters investigated. HUTCHINSON,' petchY2 and worthington3 have investigated the grain size dependence of the upper yield stress (uUYP) and the yield point drop, ouyp - aLYP, in Armco iron, mild steel, and Si-Fe, respectively. These authors used center-annealed wires to avoid stress concentration from specimen shoulders and to ensure uniformity of the applied stress. Coarsegrained specimens show no yield point drop; the yield point drop then increases as d-'I2 increases (where d is the grain diameter). These results can be understood in terms of Petch's analysis2 in which the magnitude of amp depends on the strain rate in the (limited) number of grains deforming plastically at the upper yield point. If N grains per unit volume are undergoing plastic deformation, the strain rate in the deforming grains is l/Nd3 times higher at the upper yield stress than when the whole specimen deforms homogeneously. If N is constant and independent of grain size at uUyp, then all the grains are deforming when ~d~ = 1, so there is no yield point drop. At finer grain sizes, the yield point drop is given by: where AU, is the friction stress increase corresponding to a tenfold strain rate increase. Christ, Smith, and Burton studied the upper yield point in 0.050-in.-diam wire specimens prepared from zone-refined iron. Each end of the 2; -in. specimens was soldered to a & -in. diam steel ball and the load applied through the two balls. There was a yield point drop in specimens with grain diameters less than 0.1 mm; no drop was observed in specimens of grain diameter greater than 0.1 mm that were free from veining substructure, but specimens of grain diameter 0.129 mm, annealed in the y range, showed an upper yield point. and this was associated with the presence of a veining substructure in these specimens. Christ et al. suggested the upper yield point occurs when more than a specific number of grains fill the specimen cross section so a multiplicity of slip is required to initiate plastic deformation. Table I summarizes the published data on the grain size at which the yield drop disappears. On the basis of this data the ratio of specimen diameter:grain diameter = 5 to 27 appears to be the critical value for the occurrence of a yield point drop. Thus, petch2 interprets the appearance and magnitude of the yield point drop in terms of the limited number of grains deforming plastically at uuyp, whereas Christ et a1. consider that the occurrence of the yield drop depends on the ratio specimen diame-ter:grain diameter. The published data cover a wide variety of materials so some variation between the results is to be expected, but the size range covered in the data of Table I is rather limited. In an attempt to discover whether the specimen diameter:grain size ratio or the grain diameter is critical in determining

Jan 1, 1969

By P. van Meurs

This paper describes a technique which permits visual observation of oil displacement processes througlrout the interior of a porous structure as thick as 2 in. A model having glass walls is filled with finely powdered glass. Such a model becomes completely transparent if the powdered glass pack is saturated with an oil having the same refractive index as the glass. When water or gar, with a refractive index different from that of the oil (glass) is injected, the model becomes opaque in the space occupied by the water (gar). visual observation and photography of these displacement processes are thus rendered possible. The following processes have been studied: (I) displacement of oil by water (linear drive) in a homo-geneous formation and in a stratified formation, (2) water flooding (five-spot well pattern), (3) solution gas-drive process, and (4) oil-bank formation. INTRODUCTION Most of the scaled model experiments heretofore carried out in the Koninklijke/Shell Laboratorium, Amsterdam, have been done in steel containers, in which oil-saturated sand packs represented the oil-bearing formation. In such experiments, for instance those on the displacement of oil by water, the cumulative oil production was measured as a function of the cumulative water injection. In order to interpret the measured production data, a need has for some time been felt for a means of observing visually what happens in the course of such experiments. Some information of this kind was obtained earlier by observing the water-oil distribution in various cross sections of the sand after the conclusion of the experiment.' However, the technique used did not guarantee that the fluid distribution remained undisturbed. Moreover, the procedure was somewhat elaborate and the information obtained limited. Therefore a new technique has been developed, which is described below. DESCRIPTION OF EXPERIMENTAL TECHNIQUE AND APPARATUS Glass models simulating part of an oil reservoir are filled with ground Pyrex glass of a specific grain size, representing the porous structure of the prototype. Before an experiment is started, the porous formation has to be saturated completely with an oil having exactly the same refractive index as the Pyrex glass powder. All light-scattering surfaces of the glass grains become invisible and the formation is then transparent. If the oil is displaced by another fluid (e.g. by water in a water-drive experiment, or by gas liberated from the oil in a solution gas-drive experiment) the formation becomes opaque in the region where the oil is expelled from the rock.* The back of the apparatus is painted black and illumination is from the front; therefore, in the photographs of the experiments, the oil-bearing formation appears black, whereas the water- or gas-invaded areas are white.

Jan 1, 1958

By J. M. Roberts, D. M. Barnett

The activation energy required to break a pinned dislocation line away from its condensed atmosphere of impurity atoms is calculated as a .function of applied stress, without neglecting line tension. Reasows are presented for not assuming the effect of line tension to be negligible when considering the problem of freeing a small segment of dislocation from an impurity atmosphere. The dislocation is considered to he pinned at each atomic size along its length and the pinning points are assumzed immobile. The development is a refinement of the origznal cottrell-bilby1 theory. The solution is compared to recent approximations developed by cottrell3 and Haasen5 in which line tension con- IN 1949 Cottrell and bilby1 considered the problem of determining the force required to pull a dislocation away from its condensed atmosphere of impurity atoms. They also examined the effect of thermal fluctuations on this force. The dislocation line was pictured as bowing out in a triangular loop under the action of an applied stress, and the activation energy necessary to free the dislocation from its atmosphere was calculated as a function of stress, line energy, and dislocation-solute atom interaction. siderations were neglected. A qualitative explanation of the yielding process in terms of the activation of Frank-Read sources is presented, but the lack of a realistic solution to the dynamic dislocation problem involved prevents an extension of the model at present. A self-consistent correlation between the present calculations and experimental data for delay time associated with yielding and the temperature dependence of the upper yield stress was made. Favorable agreement was noted. It is concluded that extension of the original Cottrell-~ilby' theory which includes line tension effects can just as well describe the yielding process as other approximations3,5 which neglect line tension. Cottrell and Bilby found the form of the activation energy vs stress curves to be almost independent of the line energy and the interaction energy (i.e., these parameters only affected the activation energy U by a scale factor). A check of the theory was accomplished by comparison with the experimental data of McAdam and Mebs2 for the lower yield stress as a function of temperature. cottrell,3 in 1957, attempted to obtain a simple closed-form solution for the activation energy as a function of stress by linearizing the quartic equation relating displacement of the dislocation line and applied stress. It was argued that since the contribution to the line energy/atomic plane of a dislocation is made by the long-range stress field of the dislocation through a term of the type (Gb3/2p)ln A/ro, where

Jan 1, 1963

By H. W. Hockin, D. r. Brandt, R. H. Walsh, P. L. Dietz, P. R. Girardot

New Jersey, Florida, and Canadian ilmenites were reduced with hydrogen or coke under various experimental conditions and the phase changes occurring in the ilmenite upon reduction have been studied by microscopic examination of polished sections and by X-ray diffraction. The products formed were dependent upon the type of ilmenite, temperature, time and reducing agent. Of the reducing agents, hydrogen was the more effective at lower temperatures. 1 HE possible utilization of ilmenite as a source of both iron and titanium has resulted in the development of a number of methods for the separation of the iron and titanium content. Slagging processes as currently used in Canada are typical of such methods. Somewhat less attention has been given industrially to the reduction of the iron content at less than the slagging temperature. Although references maybe found to such work, in general only one type of ilmenite, either natural or synthetic, has been studied by each author. We have attempted to draw some relationship between the results of experimental reduction and the type of deposit from which the ilmenite was derived, as evidenced by phases occurring in the ores and in the reduction products. Ilmenite ores having from 27 to 61 pct titanium dioxide were included in this study and in each case reduction was carried out at such temperatures that only limited coalescence of the particulate iron product occurred within the ilmenite grains. The history of the individual ilmenite samples and the temperature of reduction were found to determine the occurrence of various phases and the mode of distribution of the iron. REVIEW OF EARLIER WORK ON REDUCTION One of the earliest references to the reduction of ilmenite at less than the slagging temperature was made in 1917.' The metallic iron produced was_____ leached out by the action of dilute sulfuric or hydrochloric acid, to leave a product high in titanium dioxide. Subsequent to this, numerous patents2-'? and other references13"21 have appeared concerning reduction of ilmenite by carbon, hydrogen, carbon monoxide, methane, coal gas, water gas, or the like in the absence of fluxing agents. Mineragraphic examinations were not reported, and in the main, the only examinations made were chemical analyses. However, in two cases3,13, titanium suboxides were reported in the products and in one case2' rutile was reported, in addition to metallic iron. Both were identified by X-ray diffraction. While reductions in the absence of fluxing agents were generally followed by either a wet or dry chemical process for removal of the metallic iron, a Canadian source17 reported removal of the metallic iron by magnetic separation. By the addition of fluxing agents during reduction, the metallic iron has been coalesced into "pearls." Each reference to such a process23-28 has shown that the coalesced iron could be removed by magnetic or gravity means after the product was crushed. In the absence of fluxes, the coalescence did not generally occur. The major part of the present study has been limited to reductions without fluxing agents in order to determine the primary reactions of naturally occurring ilmenites. Titaniferous iron ores have also been studied,29-33 17, l9 their reduction having been used as the basis of a commercial process for beneficiation of such ores in Norway29 and more recently considered in the United States34,35. The ease of reduction of titaniferous iron ores relative to that of hematite or magnetite has been referred to,33 with the conclusion that the more

Jan 1, 1961

Discussions of the paper of Mr. Gayley read by title at the Lake Superior hieeting, but first presented at the New York meeting of the Iron and Steel Institute, October, 1904 (see p. 746). With the exception of Mr. Pourcel's discussion (p. 1038), these papers are here published under a mutual agreement between the Councils of the two Institutes, and will also be found, with others, in the Journal of the Iron and Steel In-slitute for the pear 1904, Mr. E. Windsor Richards, Past-President,' said that in 1799 Mr. Dawson, of Low Moor, read a paper before a scientific society in York pointing out the great diff'erence in the moisture of the air going into the blast-furnace in the hot months of the year and in the winter months. A cold blast-furnace was a very sensitive instrument, and showed this very clearly, for in June, July and August the furnace did not drive so well; it did not make the quality of iron and required more fuel; so that Mr. Gayley was on the right road to effect an enormous improvement in this direction. He considered that Mr. Gayley was on the way to great success, and hoped that the apparatus would not be a very expensive one. He supposed it mas too early for Mr. Gayley to let them know what the saviug was

Jan 1, 1905

By Lewis A. Riley

I desire to submit, for the consideration and information of the members of the Institute, the following data, drawings, and tables, showing what I believe will be interesting information with regard to the diamond drill, and its uses in developing mineral lands. I would first say that the results given have been obtained during the past two years by means of two drilling machines belonging to the Lehigh Valley Coal Company, operating on their coal lands in the Mahanoy, Lehigh, and Wyoming regions. 1st. A tabulated statement, giving location of borings, date, progress, total cost, itemized cost per foot, etc. 2d. Section showing strata bored in Nos. 5 and 10 holes at Mt. Carmel, see Plate VI. 3d. Section showing strata bored in No. 19 hole at Hazleton, see Plate VI. 4th. Photograph and description of drill No. 2. From the first it will be seen that the total number of test-holes bored up to May 1st of this year is 24; 9 of these are in the Mahanoy region, 6 in the Lehigh region, and 10 in the Wyoming region, in all of which cores have been taken for the whole distance. The total distance bored is 9902 feet. The majority of the holes have been put down for the purpose of proving the lower veins of the coal series, and have had to encounter the harder rocks of the coal formation. Much of the distance has been through the lower conglomerates, going in some cases through the coarse egg conglomerate, the foundation of the coal deposit, and to the green sandstone and red shale which underlie it. These lower sandrocks and conglomerates are among the hardest known to geologists, and present a formidable resistance to the exploring drill. This fact must be taken into consideratiotl in comparisons of cost of drilling, and when considered will still further improve the very favorable results I am able to show in my statement of costs. In illustration, I will cite the work of one bit when boring in the upper or softer rocks of the Wyoming region, where 280 feet were obtained without resetting, while in the Lehigh and Mahanoy regions, in the lower and harder rocks, bits set with the same quality of diamonds would only bore from 3 to 20 feet before being worn out. In this connection it may

By C. A. Mitke

(Butte Meeting, August, 1913.) 1. Character of Gases which Caused Helmets to Get Out of Order. DURING September, -1911, the fire area in the Lowell mine continually increased and gases resulting from the fire came through the upcast shaft. These gases contained such a large percentage of sulphur dioxide that the men were unable to go up and down on cages, and, within a comparatively short time, repairs in the shaft were found to be necessary. Since the fire was in sulphide ores and extended into certain timbered sections, the gases contained varying amounts of SO2 CO2, and perhaps, at times, CO. The temperature in the shaft was generally about 97°, and the relative humidity from 97 to 99.5 per cent. The corrosive action of the fumes became apparent when the cables had to be changed more often than usual, the heads of lag screws .in the guides of the shaft disappeared, and the cages needed frequent repairs. It also became necessary to repair two compartments of the shaft by putting in 150 ft. of new guides between the 600 and 800 levels and lag screws in nearly all the old guides from the surface to the 800 level. 2. Ordinary Methods of Testing Helmets which were Unsatisfactory. These conditions required all work to be done by men wearing oxygen helmets. The Draeger type was tried, and was used until all repairs were completed. At first the helmets were. tested for air circulation and air tightness and the injector was tested by water gauge according to the methods recommended by the Draeger Oxygen Apparatus Co. Six arrangements, covering .these different tests, are illustrated in the catalogue and circulars of the company.

Jan 7, 1913

By James P. Kimball

THE object of the present memoir is to put on record some practical experiments by the writer in smelting a silicious native magnetite with no other flux than the silicates of its own gangue: This work was undertaken in the spring of 1878 for Messrs. Naylor & Co., of Boston, to whom I am indebted for the privilege of here communicating its results, these having hitherto only been simply announced.* So far as I am aware these are the first instances of the kind in this country that non-calcareous; or rather non-carbonated, magnetites have successfully been used strictly alone as self-fluxing ores in the blast furnace; that is, without the addition of calcareous flux in the form either of limestone, quicklime, calcareous ore, or basic (calcareous). slag. Previous to the spring of 1878, when the Chateaugay magnetic ore was first brought to my notice, its use had been limited to Catalan forges, after "separation" at the ore bed. The blooms and billets made from it in the several forges of Messrs. Weed & Williams, and of Mr. Williams, were well known in the trade as among the best in the market. The Chateaugay ore beds proving of great magnitude, and the ore exceptionally low in phosphoric acid, it commended itself for blast-furnace purposes to Messrs. Naylor & Co., who employed nee to blow-in the charcoal furnace at Pittsford, Vt., on this ore in the spring of 1878., a previous trial of this ore in the same furnace in the fall of 1877 having proved abortive. This was therefore the first time that Chateaugay ore was successfully smelted in a blast furnace, although since well known as a blast-furnace ore possessing superior and exceptional qualities. The Pittsford furnace, although rebuilt in 1844, and subsequently improved by the former owner, the late J. Prichard, is one of the few furnaces of the old type with open breast (Sumpfofen) still active in this country. Its improvements on furnaces of the period, * Bulletin American Iron and Steel Association, XII, 1878, 132, 156.

Jan 1, 1881

By R. S. Dean. J. R. Long T. R. Graham, Roberson A. H., Armantrout C. E.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig' ') has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By Armantrout C. E., R. S. Dean. J. R. Long T. R. Graham, Roberson A. H.

The general program of the Federal Bureau of Mines on the study of alloys made with electrolytic manganese has been extended to copper-manganese-aluminum alloys. The initial results of the work are presented in this report and concern a determination of the mutual solubilities of these three metals to form the alpha solid solution. The principal studies of this system, reported in the literature, have been focused on the Heusler alloys containing ro to 30 per cent Mn with 9 to 15 per cent Al. These investigations concern the ferromagnetic properties and the determination of the crystallization contours, with little emphasis on the phases present in the solid state outside of this area. Heuslerl recognized a breakdown of the beta solid solution of the magnetic alloy, which he says decomposes into the alpha, beta, and gamma phases of the copper-aluminum system, somewhat modified by the presence of manganese. Rosenhain and Lantsberry2 examined alloys ranging up to 10 per cent Mn and 10 per cent A1 but were unable to reach definite conclusions concerning the phase boundaries in that area. Krings and Ostmann3 made magnetic studies and examined the system by thermal analysis. They present contours of the liquidus surface but do not place any of the phase boundaries. Corson4 has drawn a hypothetical boundary for the alpha field with few, data to support such construction. The binary systems involved have rcceived considerable attention by numerous investigators, and their general features are well established. The copper-ahminum system (Fig. I) has been thoroughly examined by Stockdale,5 who places the limit of solubility of aluminum in copper at 7.4 per cent at the liquidus and 9.5 per cent at room temperature. Smith6 established the eutectoid temperature at 570°C. by a study of isothermal decomposition of the beta phase. The copper-manganese system (Fig' ') has been recently reviewed by Dean and CO-WorkersS.7 Using high-purity alloys,

Jan 1, 1947

By A. Gittens

In two recent papers stevens13,14 has compared the methods used by various investigators to calculate the contribution of grain boundary sliding to the total creep strain. In previous work Gittins15 has shown that the strain due to grain boundary sliding Egb may be estimated from the lateral, d, and vertical, v, displacements of a longitudinal marker line as it crosses a grain boundary. He obtained the formula, where nL is the number of grains per unit length measured on the specimens before creep, and \p and ?2 are, respectively, the angle between the grain boundary and the stress axis in the plane of the surface and normal to the surface (see Ref. 13, Fig. 1). The subscript L indicates that observations are made in a longitudinal direction parallel to the stress axis. It was generally found more convenient to measure the grain size of a specimen before creep; this was necessary to characterize the specimen. Stevens13,14 however prefers to define Egb in terms of NL, the number of grains per unit length after creep. Since nL - NL(l + €1) where cr is the total strain, Eq. 1 11 becomes The quantities d and ?, can be determined directly from the marker lines, while v and ?2 are found by sectioning normal to the surface. In the interior when symmetry considerations suggest that v = d and ?1 - ?2 the strain due to grain boundary sliding may be estimated from a suitable internal longitudinal marker line by the equation To determine cgb at the surface using either Eqs. |1| or [2] requires a large number of observations, particularly if many estimates of cgb are required, and also it is impossible to determine the variation of cgh with creep strain on the same specimen because the specimen must be sectioned to determine ?2. Gittins15 found that for a number of materials the sliding vectors d and v were related to each other so that provided one was measured the other could be estimated. Also during creep, grain boundaries tend to migrate to meet the surface at angles close to 90 deg,16 so that the term nL(v/tan?2)L was comparatively small when 4,- 90 deg. By determining the frequency distributions of ?2 on control specimens this term can be estimated without sectioning the creep specimen. In this way an empirical equation based on Eqs. |1| and |2| enables cgb to be determined with reasonable accuracy with fewer observations of the angles and sliding components. For B brass, the relationship between the sliding vectors indicated that ceb = 0.85nLVL . In Table I of Stevens paper this equation is stated to be incorrectly derived. However it should be pointed out that this is an empirical equation derived from Eq. |1|, based on a knowledge of the relationship between d and v and on the frequency distributions of ?1 and ?2 for a particular material under given experimental conditions. It was used only when these relationships were known, to reduce the number of observations required to estimate cb. Therefore the comment "derivation incorrect does not apply. Gittins did in fact make use of Eqs. |1| and 131. Author's Reply I must apologize to Dr. Gittins for the inadvertent misrepresentation of his work. Other slight errors in Table I have been pointed out to me. Langdon (No. 12 Table I), Gifkins (No. 7, Table I), and possibly other workers did not measure the number of boundaries per unit length after creep (A') but the corresponding quantity bejove creep (n). As Dr. Gittins points out, a completely analogous set of equations to those given in the paper can be derived by the same method: using the number of boundaries per unit length before instead of after creep. The basic equations corresponding to Eqs. [2] and 171 of the paper, from which all the others can be derived, are

Jan 1, 1968

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 William R. Webster

An investigation has been made of 500 samples of universal and sheared plates of basic Bessemer and basic open-hearth steel manufactured by the Pottstown Iron Company, the carbon-limits being 0.07 to 0.18 per cent. Through the courtesy of Mr. W. H. Morris, President, I am able to lag before the Institute the results of these tests. The samples tested were all taken from the finished material, and the chemical determinations were made on drillings from the broken test-pieces, which were sent to the chemist without giving him the heat-numbers. The results are such as to encourage me to keep on with the work, and, if possible, to have it carried out on other steels. It is kith this view that I now offer my tables in their incomplete form. My first table mas constructed by grouping the tests according to chemical analysis in various. ways, and making a rough tabulated statement, from which the ultimate strengths were worked out and carefully compared with the actual results of the tension-tests. From data thus obtained, one table after another was worked out, and by this method of "cutting and trying" I finally arrived at the results which I now present in Table I. (p. 771). I do not claim absolute accuracy, but my approximations have proved to be so close that the figures are practical data for current use at the works. The indications are that a pure iron, without carbon, phosphorus, manganese, or silicon, if it could be obtained, would give 38,000 pounds ultimate strength. This is assumed as a base, and to it is added the effect of each of the above elements, as explained below. The upper part of Table I. gives the ultimate strength due to carbon and phosphorus, and is the same for both basic Bessemer and basic open-hearth steels. The lower part gives the increase in ultimate strength due to manganese. By adding this to the amount obtained from the upper part, we have the ultimate strength of basic Bessemer

Jan 1, 1893

By S. Beatty

RECENT experimental results' on the superconductive properties of vanadium indicate that the magnetic behavior of the metal is greatly affected by internal strains caused by mechanical work, and particularly by oxygen and nitrogen impurities. These result in an increase in the hardness of the metal such that metallurgists' have used hardness as a measure of the impurities. An increase in the impurities should also be reflected in a change of lattice parameter with increasing impurity content. The lattice parameter of vanadium prepared by the thermal decomposition of the iodide has been determined by two workers. Neuburger3 obtained a value of a, =3.0338 ± 0.0003A for the body-centered cubic lattice by means of the powder method. The work of Katelaar is referred to by van Arkel4 in which a value of a0 = 3.025 is given. Four samples were used for this investigation. Sample A, the vanadium of the highest purity in the group, was obtained by means of the thermal decomposition of vanadium diiodide and deposited on a 3 mil diam tungsten filament in the form of crystals. The second sample, labeled B, was obtained by the calcium reduction of the pentaoxide at a sufficiently high temperature to give a melt. A third sample, C, was obtained in the same manner as B but remelted in a pure argon atmosphere. The last sample, D, was prepared by the calcium reduction method and the fine powdered vanadium was then sintered by means of applied heat and pressure. Samples A, B, and C were thus essentially free of mechanical strain in their preparation. Sample D was annealed in a high vacuum at 800°C. The samples were prepared for X-ray diffraction analysis such that all additional strain by cold work or by contamination with oxygen and nitrogen was kept at a minimum. Powder obtained from filings was deemed unsuitable since this would require annealing to get rid of the cold work. A heat treatment up to 1000°C at 10-6 m pressure might still increase the impurity content by means of adsorbed oxygen from residual gas in the vacuum chamber. The most satisfactory samples were prepared for back-reflection film techniques. Samples were cut to size, etched with hydrobromic acid, and mounted in Bakelite. They were then lightly polished on 3-0 paper and lightly etched. Chemical and Hardness Analysis of Samples Spectrographic analyses were made of the four samples and indicated similar metallic impurities for the group. The major metallic impurity in each sample was iron, which was less than 0.01 pct. The sum of the other metallic impurities was approximately 0.1 pct. The carbon content was assumed low by virtue of the methods of sample preparation. The principal impurity difference between the samples was in the oxygen and nitrogen content.

Jan 1, 1953

By W. R. Seyfried

THE problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations. An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper. The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reagent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp. became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant. By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1472°F), (b) The roasted ore would then be leached with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1947

By C. T. Eddy, R. W. Drier

The conductivity of copper wire is of prime importance to the electrical industry and consequently to the copper refiner and wire manufacturer. Annealed copper wire has a higher conductivity than hard-drawn wire, but, on the other hand, its tensile strength is lower. In an attempt to explain the reasons for these changes in properry. or at least to study the conditions existing in these two types of copper wire, the experiments described here were carried on in the Department of Metallurgy of the Michigan College of Mining and Technology This is only a partial and preliminary report on some of the work done to date on a research program of which the object is an intensive study of copper. It is offered with the hope that, though it is not an exposition of the most rigorous of conclusions, the general trend of inferences which may be drawn will be of value and interest. Effect of Direction of Drawing In 1928 some work was done on hard-drawn copper wires to determine whether wire drawn in a continuous machine (that is, all in one direction) would have a different structure from wire that had a reversal in direction at some stage of the drawing process. The diffraction spectra obtained indicated that as the position of the wire rayed approached the core, a preferential crystal orientation existed, and that the closer to the core the more preferred was the orientation. The data obtained partly corroborated the work done by Schmidt and Wassermanl and by Clark.2 Samples Used in Following Investigation The samples selected for use in both the diffraction work and the resistivity measurements were taken from Nos. 6, 8, 10 and 12 gage

Jan 1, 1930

By B. J. Bayles, J. A. Ford, M. J. Salkind

Unidirecltonally sulidijied AL-A13Ni was found to exliibit excellent microstructural stability to 508°C. Above this temperature the transverse micvostructure coarsened in a manner analogous to "Ostwald Ripening", but the A13Ni whiskers did not spheroidize or foreshorlen. The coarsened whiskers reinforced the matrix as effectirely as the finer whiskevs and no reduction in room-temperature tensile strength mas noled after exposure for 90 hr at 96 pel 0-1 the absollite melling temperature of the eulectic. The slability was auribucted to the presence of low-index (and presurrlably lor-energy) cvystallographic interjaces between phases. The driving force for microstructural coursening was presumed to be the reduction of interfacial energy between the phases. Finer micvoslructures were found to coarsen more rapidly than those which weve imitally coarser. FIBER-reinforced metals have been shown to exhibit good short-time tensile properties at elevated temperatures.1-4 However, many elevated-temperature applications require long-time property retention which dictates the necessity for microstructural stability. Two types of instability are common to fiber composities. The first, chemical instability, is due to chemical reaction between the matrix and the relnforcing phase. Petrasek and weeton5 have shown that chemical reaction between tungsten wire and several copper alloy matrices resulted in degradation of the reinforcing phase and reduction in strength of the composite materials. Kreider and Leverant4 have noted similar behavior for boron-reinforced aluminum above 400°C. The second type of instability arises in systems in which the phases are essentially chemically stable with respect to each other and is characterized by spheroidization and/or agglomeration of the reinforcing phase. parratt6 has reported this type of degradation to occur relatively rapidly at moderate temperatures for nickel and cobalt alloys containing whiskers of silicon nitride, aluminum oxide, and silicon carbide and has identified it as "physicochemical" instability. Although both types of instability are the result of the differences in the chemical potential between the fibrous phase and the matrix, they may be differentiated by the fact that the second type, "physicochemi-call' instability, results in little or no net change in the composition or amount of each phase present. It does, however, result in a morphological change which profoundly affects the strengthening mechanism. Chemical interaction. on the other hand, results in a change in the composition and amount of one or more of the phases present, or the appearance of a new phase. In the latter case, the appearance of the mi-crostructure, that of a fibrous phase aligned in a matrix, may remain essentially unchanged, but the chemical degradation of the fiber results in markedly reduced composite strength. This investigation was initiated in an attempt to evaluate the microstructural and related mechanical property changes of a whisker-reinforced eutectic composite after elevated-temperature exposure. The composite system chosen for this study was the uni-directionally solidified A1-A13Ni eutectic which Lemkey. Hertzberg, and Ford7,8 demonstrated to behave as a whisker-reinforced composite. The microstructure of the unidirectionally solidified material consists of aligned needles of A13Ni in a matrix of aluminum. EXPERIMENTAL PROCEDURE Eutectic ingots having a nominal composition of 6.2 wt pct Ni were produced by melting 99.99+ pct A1 and 99.99 pct Ni in recrystallized alumina crucibles in an argon atmosphere. The analyses of the starting materials are listed in Table I. These master heats were cut up? melted by induction heating, and unidirectionally solidified vertically in 1/2 -in.-ID. 6-in.-long graphite crucibles, in a dynamic argon atmosphere. Therma1 gradients in the liquid were determined by measuring the temperature in the melt as a function of apparatus travel distance, as discussed by Kraft and Albright.9 The rate of solidification was assumed to be equal to the uniform rate at which the crucible assembly was withdrawn from the furnace. Ingots representative of nominal growth rates of 2, 5, and 11 cm per hr were produced and the solidification parameters are summarized in Table 11. Ingots used for met allographic analysis were pre-

Jan 1, 1968

By J. V. Gluck, Ping-Wang Chiang

The tellurium-rich region of the Sb-TI-Te ternary system was investigated by means of DTA, metallo-graphic, X-ray, and electron beam microprobe techniques on the sections Sb2Te3-T12Te3, SbTlTe2-Te, SbT1Te2-Sb2Te3, and SbTlTe2-T12Te3. The phase behavior of this region is summarized in terms of four ternary invariant reactions and a schematic reaction diagram is suggested. Isopleths for the sections SbT1Te2-Sb2Te3, Sb2Te,-T12Te3, and SbTlTe2-Te were constructed, and a schematic diagram of the projections of the liquidus lines and invariant planes is presented. No evidence was found to support the existence of the ternary compound "SbTlTe3", or pseudo-binary behavior of the section T12Te3-Sb2Te3, as reported by Borisova and Efremova. Electrical conductivity, Seebeck coefficient, and thermal conductivity measurements were made at room temperature on fully annealed samples. 1 HE phase relationships in chalcogenides are often complex and difficult to resolve, particularly since the approach to equilibrium is a rather slow process. For example, the phase diagram of the T1-Te binary system was in doubt until clarified by Rabenau et al.,1 the phase fields at compositions near Bi2Te3 in the Bi-Te binary system have only recently been satisfactorily elucidated by Glatz,2 and there may still be some question as to the extent of the Sb2Te3 field in the Sb-Te system.3-5 In ternary systems, the existence of the compound "AgFeTe2" was the subject of a number of conflicting reports6-8 and the stoichiometry of the composition "AgSbTe2" was in doubt for a period of time.9 Recently, questions have arisen regarding the existence of certain compounds in the ternary systems Bi-Tl-Te10-14 and Sb-Tl-Te.15 The impetus for studies of these latter systems stemmed from the report of Borisova et a1.10 of a congruently melting ternary compound, "BiTlTe3", which apparently had extremely favorable thermoelectric properties for room-temperature cooling applications. Attempts by other investigators to produce the compound or confirm the transport properties proved to be unsuccessful.12-14 Recently, Chiang and Gluck14 reported studies of the phase relations in the tellurium-rich region of the Bi-T1-Te system which indicated that the section T12Te3-Bi2Te3 was not pseudobinary as suggested by Borisova et a1.10 The contention of Spitzer and sykes12 was supported that the composition "BiT1Te3" was multiphase, with the primary constituent actually being BiTlTe2, a compound whose existence has been well demonstrated.16,17 The investigation reported in the present paper was prompted by a later report of Borisova and Efremova15 on a similar study of the section T12Te3-Sb2Te3 from the Sb-T1-Te system. They also claimed this section to be pseudobinary, and that a ternary compound "SbTlTe," was formed peritectically. Some "preliminary" crystallographic data were given for the compound and thermoelectric transport properties were presented. In view of the questions concerning the behavior of the Bi-T1-Te system and the existence of the compound "BiT1Te3" it was suspected that the Sb-T1-Te system might behave in a similar fashion, particularly in light of the known existence of a compound SbT1Te2, iso-structural with BiT1Te2.17 Consequently, an investigation was undertaken to clarify the phase relationships in the tellurium-rich region of the Sb-T1-Te system. It is the purpose of this paper to present the results of this study, including a representation of the phase relations, isopleths for various composition sections, and the determination of some phase compositions and transport properties. EXPERIMENTAL PROCEDURES Commercially available high-purity (99.999+ pct) elements, purchased from the American Smelting and Refining Co., were used for the sample preparation. All samples were made from thoroughly mixed powders of previously prepared master alloys: SbTlTe2, Te, Sb2Te3, and T12Te3. Stoichiometric quantities of the constituents for each 10-g sample were weighed into a specially cleaned fused silica tube and sealed under a vacuum of better than 5 x 10-5 torr. The sealed constituents were fused and reacted at 650° to 750°C for at least 4 hr under continuous agitation in a "rocking" furnace, and the resulting product was air-cooled. The tube was opened and the sample was ground to a powder. A portion of the powder was rebottled in a DTA tube under vacuum, and the rest of the material was similarly resealed in a separate tube, re-fused in the rocking furnace, and again cooled to make the ingots for electrical and microstructural studies. All samples were subjected to further heat treatments as discussed in the section on experimental results. Each DTA tube was made of 7-mm-OD fused silica tubing with a concentric 2-mm-ID depression about 4 mm long formed in the bottom to accommodate a thermocouple. The size of a DTA sample was 0.5 to 1.0 g. An Aminco Thermoanalyzer whose accuracy was within 2°C18 was used for the DTA measurements. The metallographic samples were prepared by conventional techniques. A solution of FeCL dissolved in a methanol-HC1 mixture was found to be the most satisfactory etchant. Electron beam microprobe scanning and point-count examinations were made on polished and unetched samples using an ARL Electron Microprobe at an electron beam voltage of 20 kv. The detectors were set to receive characteristic La1 radiation. Calibration standards of the pure elements were incorporated in each sample mount; quantitative point counts were calibrated by a method similar to Ziebold

Jan 1, 1969

By C. H. Curtis

HE valuable mineral content of the current feed -*- to the Miami concentrator is as follows: copper, 0.7 pct total; molybdenum, 0.01. Flotation of this ore yields a sulphide concentrate containing: chalco- cite, 44 pct; molybdenite, 0.5; pyrite, 50.0; insol, 5.5. A combination of potassium ethyl xanthate and pentasol amyl xanthate as collectors, and pine oil as frother, are used in this flotation. Rejection of pyrite is encouraged by holding the amount of collectors used to the minimum consistent with copper recovery and by operating at high alkalinity (equivalent to 0.35-0.40 lb CaO per ton solution of pH 11.0). The molybdenum recovery in the sulphide concentrates under the above flotation conditions is approximately 50 pct of that originally present in the ore. Taking into account the acid soluble molybdenum, indicated molybdenite recovery is 75 to 80 pct. The attempt to separate the molybdenite into an acceptable molybdenum product begins with the bulk sulphide flotation concentrate just described. This concentrate is composed of chalcocite, whose floatability has been promoted to the fullest extent possible for the sake of its recovery from the ore, together with the pyrite which has been activated along with the copper mineral. The problem is to deaden the copper and iron minerals, and to float the molybdenite. Obviously in the accomplishment of this end, conditioning and preparation of the pulp, prior to flotation, plays an all important role. The first step is thickening to 50 to 60 pct solids, with milk of lime added to the thickener feed to maintain an alkalinity of the pulp equivalent to a pH of 8.5 to 8.8 during its residence in the thickener. The purpose of the thickening is primarily to reduce the volume of pulp for subsequent treatment. However, the relatively prolonged retention of the pulp in the thickener at the desired alkalinity is known to have a favorable depressing effect upon pyrite. There is a limit for this alkalinity above which a depressing effect upon molybdenite occurs. The thickened pulp (alkalinity: 0.015 lb CaO per ton, pH 8.8), discharges into an agitator, retention time approximately 2 hr, to which additional lime is added to raise the alkalinity to 0.35 to 0.40 lb CaO per ton solution, pH 11.6. This additional lime is required for pyrite depression and can be tolerated without loss of molybdenite because of the limited time of contact in the conditioner tank. The pulp leaving the lime conditioner passes through two successive steaming tanks, which are mechanically agitated, and into which live steam is admitted directly into the pulp near the bottom of the tanks. The temperature of the pulp is maintained as near boiling as possible. The steaming time is approximately 4 hr. The pulp leaving the last steamer has an alkalinity of about 0.04 lb Cao per ton solution, pH 8.7. It is believed that oxidation of the copper and iron sulphides occurs during steaming, the resulting sulphates reacting the calcium hydroxide to calcium sulphate and thus reducing the alkalinity. Since the steamer-feed solution is already saturated with calcium sulphate, the calcium sulphate produced during steaming is precipitated. It is believed that this calcium sulphate is precipitated preferentially on copper and iron mineral surfaces thus decreasing their floatability. Aside from the "lime chemistry" during steaming, pine oil is displaced from the pulp and xanthate decomposed, which has a major effect upon the deadening of the copper and iron sulphides. Following steaming, the hot pulp is admitted to another conditioning tank wherein it is aerated, primarily for cooling, but incidentally for additional oxidation of the copper and iron sulphides. The resulting "deadened" pulp is then diluted to 20 pct solids, a specific collector for molybdenite, ordinary stove oil, is added and the separation of the molybdenite by flotation is undertaken at a pH of 8.5 to 8.8 in standard Miami air-flotation ma-chines. B-22 frother is used when necessary. A re-grind of the thickened rougher concentrates is made prior to the first cleaning operation chiefly for rejection of insoluble in subsequent flotation. The cleaner concentrate is then stepped up to 90 pct MoS, in an 8-cell Denver flotation machine No. 18. Sodium silicate is added to the cleaner circuit. Its effect is to flocculate molybdenite and stabilize the froth. In summary, it may be stated: 1. Separation of molybdenite into an acceptable product from sulphide copper concentrates by flotation involves preliminary preparation and conditioning of the pulp, which is of major importance. 2. This preparation and conditioning consists of several successive steps: (A) Thickening to 50 to 60 pct solids at controlled alkalinity to reduce volume of pulp and to contribute to depression of pyrite. (B) Agitation at high-pulp density for limited time with additional lime to provide for depression of pyrite. (C) Steaming at high-pulp density for decomposition of xanthate and xanthate surface films, evolution of pine oil, and oxidation of sulphide minerals other than molybdenite. The latter involves sulphating of lime with probable precipitation of calcium sulphate preferentially on copper and iron minerals. (D) Aeration at high-pulp density for cooling, and for further oxidation of copper and iron sulphide minerals. (E) Dilution of pulp to 20 pct solids and addition of specific collector for molybdenite, common stove oil. It is hardly necessary to point out that this rather drastic procedure for depression of previously activated copper and iron sulphide minerals, without at the same time depressing molybdenite, is possible due to the inherently high floatability and refractory nature of molybdenite. However, molybdenite is susceptible to depression by excessive lime which must therefore be limited to the amount consistent with satisfactory molybdenite recovery. The steaming procedure is being carried on at Miami Copper Co. under license agreement with Janney, Nokes, and Johnson, holders of letters patent on the process.

Jan 1, 1951