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By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By Henry A. Gordon

Under the title " Hysteromorphous" it is proposed to include deposits which have been formed from original deposits by the influences of the surface-region. The term Hysteromorphous—later-formed—has been used by Prof. Posepny, of Vienna, to distinguish secondary from primary deposits and is more comprehensively applicable than the terms or designations hitherto used for the same thing.

Jan 1, 1896

By William M. Kester

INTRODUCTION The Coal Research Bureau of the School of Mines at West Virginia University is presently conducting laboratory-scale tests to determine the technical feasibility of beneficiating pulverized coal and coal fines with high-intensity electromagnetic fields. Interest in magnetic processes for cleaning fine coals was stimulated by results obtained by Yurovsky, et a1 in 1958.1 This work, while not new in concept,2,3 indicated that pulverized coal which had been thermally treated in a rotary drum in the presence of superheated steam and air underwent thermo- chemical reactions. Films of the ferromagnetic minerals magnetite (Fe2O3), hematite (Fe3O4), and pyrrhotite (FeS[3]) were reported to be formed on the surfaces of the pyrite grains associated with fine coal during the foregoing treatment at temperatures ranging from 120 to 360°C. After thermal treatment the coal was magnetically separated in an experimental magnetic device having a field strength of 10,000 oersteds.

Jan 5, 1965

By Shiro Ban-ya, John Chipman

The effects of many alloying eletnents on the acticity coefficient of sulfur in liquid iron have-been studied by the equilibriutn in the reaction Sfin Fe) + Hz = HzS at 1550°C'. Results are expressed in terms of a concentration variable for a nonmetallic or for a substitutional metallic solute. Activity coefficient of sulfur, defined as increased by B, Al, C, Si, Ge, Sn, P, As, Sb, Mo, W, Co, and PI. It is decreased by Cu,Au, Ti. Zr, V, h'b, Ta, Cr, ,23n, and Ni. Irulues oj. the interaction coejficient 0i = 6 In are labulated. The same interactions are expressed also in terms of atom fraction and of weight percent. The thermodynamic properties of sulfur in liquid iron have been fairly well established. Our recent paper1 reported new determinations of activity coefficient up an atom fraction of 0.12 and equations based on a careful review of all published data. The effects of alloying elements on the activity of sulfur have been studied by several investigators,2"11 especially by Morris and Williams for silicon,' by Morris and Buehl for carbon,~ and by Sherman and Chipman for manganese. phosphorus, and al~minum.~ However, the effects of some important alloying elements remain to be determined. The purpose of this investigation was to determine the effects of many alloying elements on the activity of sulfur in Fe-S-j ternary systems. EXPERIMENTAL METHOD This study was based on experimental determination of equilibrium in the reaction at 1550°C: The same apparatus and procedure as described in our previous paper have been retained, and the same corrections were applied for dissociation of H2S. The alumina crucibles used in the experiments consisted of four separate compartments. In a given experimental run. kach of three alumina crucibles held four different samples of about 3 g each which reached equilibrium in the same gas atmosphere and temperature. The charges were made up of electrolytic iron, pure iron sulfide, and desired alloying elements, which were pure metal or master alloys made in the laboratory. The weighed samples were held for 4 to 12 hr in the prepared atmosphere at 1550°C. They were then low- ered to be cooled as quickly as possible. The quenched metal beads were crushed to avoid the errors of segregation in the ingot. The sulfur content was determined gravimetrically and alloy content by appropriate chemical analysis. CALCULATIONS The apparent equilibrium constants of Eq. [I] are expressed as follows from the corrected gas ratios and sulfur concentrations: The term K" is the observed equilibrium constant in any given ternary solution, K' is the value for the Fe-S binary solution. and the limiting value of K' in the infinitely dilute solution is designated by K, which is the true equilibrium constant in Eq. [I]. In the thermodynamic treatment of nonmetallic elements in a metallic solution, it has been suggested1' that the lattice ratio has certain advantages over other variables to express the concentration of solute. In interstitial solid solutions the lattice ratio zj is proportional to the ratio of filled interstitial sites to those which remain unfilled. The equations derived for the activity of the solute using zj as the concentration variable are found also to be applicable to liquid solutions containing nonmetallic solutes when the nonmetal is treated as if it were interstitial. For this purpose we adopt the following definitions: The quantity vj which is negative for interstitial solutes is taken as -1 for nonmetallic and +1 for metallic solutes. For purposes of calculation however ; j may be assigned a value which results in a linear relation such as shown in Figs. 1 to 15. The activity coefficient of sulfur, Qs, and equilibrium constant. K(z). are defined as follows: According to a Taylor series expansion. the logarithm of the activity coefficient of sulfur in Fe-S-j ternary system is: However, the value of 6 In */6zi remains constant through a broad range of dilute solutions and the terms of higher order are negligibly small. As a consequence, Eq. [6] is simplified as follows:

Jan 1, 1970

By J. S. Browning

The U.S. Bureau of Mines has been experimenting with flotation processes to separate the spodumene-beryl ores mined at Kings Mountain, N.C. The success to date as well as the present status of the process is discussed. Further experimentation is underway and studies will be made on the milling costs involved in the flotation process. The pegmatites of the Kings Mountain-Lincoln ton, N.C., area constitute the largest known domestic reserve of beryl and spodumene. The reserve is estimated to contain 90 million tons of pegmatic material with 1,280,000 tons of recoverable Li,O(lithia) as spodurnene.' The pegmatites also contain 0.4 to 0.5 pct beryl disseminated throughout the orebodies. The pegmatites may contain a potential reserve of 240,-000 tons beryl, equivalent to approximately 34,000 tons of BeO. Different flotation methods for separating beryl from feldspar or quartz, or both, have been developed by various investigators.2-7 On the other hand, published information is limited on concentration of spodumene-beryl ores. As the response of beryl and spodumene to flotation is essentially the same, a successful separation of the two minerals depends upon use of a selective depressant or a selective collector for one of the minerals. Several years ago, the U.S. Bureau of Mines, recognizing the need for developing a large domestic supply of strategic beryl, undertook studies to develop improved methods of recovering this mineral. Because of the low beryl content of the pegmatites, economic production of the beryl entails its recovery as a byproduct of spodumene flotation. Thus, the development of procedures that would provide for maximum recoveries of the spodumene, as well as the beryl, was a primary objective of the studies. Tests were made on run-of-mine ore and spodumene flotation tailing from the Foote Mineral Co.'s spodumene concentrator at Kings Mountain (Fig. 1). Pet-rographic analyses of the ore and flotation tailing are given in Table I. Detailed analyses and examinations of the ore and tailings revealed that the beryllium was present in the form of a low-alkali beryl. The crystals were small, rarely larger than 14-mesh diam, and were clear and colorless. About 10 pct of the Li20 content of the ore was present in the mica and feldspar components of the pegmatite. In some weathered ores the associated clays also contained small amounts of lithia. This is typical of pegmatites in the Kings Mountain area. LABORATORY TESTS In the past, a vigorous chemical treatment of the spodumene surfaces with acid or caustic soda has been considered essential for satisfactory selective flotation of the spodumene from the other minerals in pegmatites. Many tests were made during this investigation to determine if chemical treatment of the spodumene could be eliminated in favor of a reagent combination that would depress the other minerals while selectively floating the spodumene. A simple reagent combination and process was developed that gave better spodumene recovery and grade of concentrate than the more elaborate acid or caustic treatment methods previously used. The finely ground ore pulps were conditioned with either an ammonium, alkali, or alkaline earth lignin sulfonate and sodium fluoride, and the spodumene was floated and cleaned using oleic acid as the collector. The spodumene tailing was deslimed, conditioned with sulfuric acid and coco amine acetate, and floated to reject mica. The mica tailing was thickened and conditioned with hydrofluoric acid, then washed to remove the acid. The washed pulp was conditioned with sodium hydroxide for pH control, and the beryl was floated and cleaned with oleic acid as the collector. Table II summarizes the results of the laboratory test work. About 77 pct of the spodumene and 75 pct of the beryl were recovered from the pegmatitic material. The spodumene concentrate assayed 6.1 pct Li20 and 0.01 pct BeO, and the beryl product assayed 3.0 pct Li20 and 1.57 pct BeO. Similar results were ob-

Jan 1, 1961

By H. M. Howe

PART I. INTRODUCTORY. § 24. INTRODUCTION.-This paper discusses the chief existing data as to the temperature, in iron-carbon alloys, of Ae.3, the upper limit of the transformation range when in equilibrium, as distinguished from Ac3, the temperature at which the end of the transformation is noted in heating up, and from Ar3, that at which its beginning is noted in cooling down. The former is in fact carried above Ae3 and the latter below Ae3 by lag. I touch incidentally on the influence of manganese on Ae3 (§ 29, p. 1102). The sections, tables, and illustrations, are numbered consecutively with those in the accompanying papers by Howe and Levy on Determination of, the Position of Ae3 in Carbon-Iron Alloys, and by Burgess, Crowe, and Rawdon on Thermal and Microscopical Examination of Professor Howe's Standard Commercial Steels, to which the present paper forms a sequel. § 25. The contradictoriness of our present evidence is shown by grouping it together in Fig. 14. For instance, both Goerens and Meyer (Series 2) and Meuthen (Series 12) used practically stationary temperature, and thus reduced the influence of lag very greatly; yet Ae3 for 0.32 carbon steel according to the former investigators is 894°, but according to Meuthen it is at or below 770°, a discrepancy of 124° or more. In view of our ability to measure these high temperatures within a few degrees, the existence of such a discrepancy is as unwelcome as it seems needless. I attack the thankless task of bringing some order out of this chaos.

Jan 6, 1913

By Haley, D. F.

WHEN operations were first started at Climax in 1917 by the Climax Molybdenum Co., they were pioneering in the molybdenum industry for little was known relative to the uses of molybdenum or the metallurgy of molybdenite concentration. Concentration of molybdenite is relatively simple today but in 1916, when the Climax deposit first attracted attention, it presented serious difficulties. Little was known, in fact, even about the assaying of such low-grade molybdenum ores. Mine samples were sent to at least a dozen of the best laboratories in the United States and average values reported varied from 0.4 per cent to 1.0 per cent MOS2. Owing to the wide variations in MoS2 content obtained from reliable chemists, the actual value of the ore was most uncertain. This variation occurred repeat¬edly over a period of six months in 1917. It was finally decided, as a last resort, to cut several tons of sample from the tunnel and have a mill test made, using the recovered MoS2 per ton as the grade of the ore, for a small error in the assaying of the concentrate would not materially affect the results. These mill tests were made by the General Engineering Co. (Callow) at Salt Lake City. The results proved an ore of commercial grade and indicated the flotation process for the best metallurgy. Based upon these tests, the decision was made to build a 200-ton flotation plant. At this time, the art of flotation was

Jan 1, 1946

By H. W. Morse

THE CHAIRMAN (H. W. MORSE).-Gentlemen, for the first time in the history of the American Institute of Mining Engineers, we have a full session on the subject of leaching-especially on the leaching of copper ores.. This branch of metallurgy is rather in its infancy. We have had one big plant running for a year or more, and pretty successfully; and another one which will be started in February or March, the New Cornelia. We have another one at Garfield for the Utah company, which is just designed and construction begun; and from several other points come reports of interesting test work. The first paper on the program this evening is one of some of the test work on the New Cornelia ore by myself and Mr. H. A. Tobelmann. LAWRENCE ADDICKS, New York, N. Y. (written discussion).-The Ajo proposition has had, as I understand it, two great advantages: it has not been obliged to measure leaching against flotation or some other metallurgical process, and it deals with a copper content high enough

Jan 12, 1916

NEW MEMBERS The following list comprises the names of those persons who became members during the period of Feb. 10, 1918, to Mar 10, 1918. ADKINSON, HENRY M., Min. Engr Walker Bank Bldg., Salt Lake City, Utah. BARKE, A. C., Min. Engr., United States Smelt., Refin. & Min. Exploration Co., 1503 Hobart, Bldg., San Francisco, Cal. BARKER, F. L., Prof. of Min. and Geol., Pei Yang University, Tientsin, China. BEASLEY, ALFRED F., Supt. Of Refinery, Bunker Hill & Sullivan Min. & Cone. Co., Kellogg, Idaho. BEEKLY, A. L Chief Geol., Cosden & Co., Tulsa, Okla. BELLIS, ARTHUR E Met., N. E. Westinghouse Co., Springfield, Mass. BRAIN, ELMER C Mgr., United Gold. Min. Co., Granite, Ore. BRUNER, CRANE S., Engr., American Zinc, Lead & Smelting Co., Carterville, Mo. COLLINS,. HARRY R Mech. Engr., Fuller Engineering Co., Allentown, Pa. CRANKSHAW, ALDEN, Experimental Met., New Jersey Zinc Co. (of Pa.), Palmerton, Pa. GALLIGAN, EMMET F., Mine Supt., Homestead-Iron Dyke Mines Co., Inc., Homestead, Ore. GREENE, FRANK C Geol., Cosden Oil & Gas .Co., Tulsa, Okla. HALSEY, HOWARD G Field Engr., 0. M. Bilharz Min. Co., Miami, Okla. HARROUN, DOUGLASS HOUGHTON, Supt.., Aguascalientes Metal Co., Asientos, Aguascalientes, Mexico.

Jan 4, 1918

By M. E. Wadsworth, W. H. Dresher, W. M. Fassell

HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.' The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.' National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 sphalerite,4 galena," and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,6 ho found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo++ in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit's construction and operation have been discussed elsewhere,' only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By P. L. Rittenhouse, M. L. Picklesimer

A rapid and seniquantitative method of determining prefered orientation on large numbers of. Zircaloy-2 specimens was desired. knoop microhardness measurerrzetzls were irvestigated as a solldtion to this pro6lem. The variation of Knoop microhardness measurerlerzts on selected planes as a function of 'irzdenle axis relutilje lo cryslallograplzic or fabrication divectals were used to corzstrrcl a polar coordinate hardness contour map. With use of an empirical relationslip between the single-crystal hardnesses and those of the polycrystalline material conentional pole figures could be constructed which compare favorably also obtained. To determine preferred oriention qualitatively from hardness data requires a minimum of twelve measurements per plane on three, preferattention to grain size, specimen prepartion, and in-rreinetzt, and analjlsis is of the order of- 45 to 60 rrin. THE design of structures from Zr alloys requires consideration of preferred orientation and the resulting anisotropy of mechanical properties. Rapid and semi-quantitative methods of evaluating anisotropy and of determining preferred orientation are needed for quality control and for examining the large number of test specimens required in development programs. The variation of Knoop microhardness with indenter orientation has been studied in single crystals of several hcp metals including titanium.' beryllium,' magneium, and zinc.4 The maximum hardness observed on any crystallographic plane other than the basal plane invariably occurred when the long axis of the Knoop indenter was either parallel or perpendicular to the projection of the [ OOOI.] direction on the plane of examination. When the major slip mode was (0001)(i2i0j the maximum hardness occurred at the parallel positio! but when the operating slip system was {10i0) (i210) the hardness was a maximum perpendicular to the [0001] projection. A minimum hardness was always observed at a rotation of 90 deg from the maximum. It follows that the orientation of the projection of the [0001] can be determined on any non-basal plane by making hardness measurements at a number of indenter orientations. The determination of the orientation of the [0001] projection on two non-parallel, preferably orthogonal, surfaces of the specimen will allow location of the [0001] direction in the specimen. It seems possible that such measurements could be used to examine, at least qualitatively, the preferred orientation existing in polycrystalline hcp materials. An investigation of the microhardness anisotropy in Zircaloy-2 was undertaken to ascertain whether these measurements could be used for this task. EXPERIMENTAL PROCEDURE Single crystals of Zircaloy-2 were grown by an a-8-a annealing sequence using electron-beam heating.= The orientation of the crystals was determined by a conventional back-reflection Laue technique. The crystals were then mounted on a goniometer head and the desired crystallographic faces were milled and chemically polished. Polycrystalline Zircaloy-2 specimens were prepared from fabricated sheets or plates. Inverse pole figures for these materials were obtained using the X-ray diffraction techniaue described by Jetter, McHargue, and illiams.' A Wolpert-Greis Micro-Reflex hardness-testing machine was used to make the Knoop microhardness measurements. The single-crystal and polycrystalline specimens were loaded to 0.5 and 2.0 kg, respectively. Determination of the scatter of hardness numbers as a function of applied load for several indenter orientations on several specimen surfaces showed that the loads selected were the lightest consistent with minimum scatter. Heavier loads did not appreciably decrease the scatter and produced hardness impressions too large to be conveniently measured with the equipment used. Seven crystallographic planes of the single crystals were examined, while six planes of examination were used in studying Zircaloy-2 polycrystals. The specimens were rotated 10 to 15 deg after each measurement and from four to eight impressions were made at each angle of rotation. RESULTS The two angles which were used to relate crystallographic directions and planes in the hcp cell to the planes of examination of the single crystals are shown in Fig. 1. 8 is the angle between the c axis. [0001]. and the normal, N, to the plane of examination. a is the angle between the long diagonal of the Knoop indenter and the projection of the c axis on the plane of examination. For exampIe, if P = 90 deg and a = 0 deg, the plane of examination is of the family

Jan 1, 1967

By George Bain

SOME problems concomitant with commercial exploitation of marble are presented as examples of interesting, useful and profitable fields for application of scientific knowledge. The marble industry is only one such field and is selected because its varying new aspects are familiar to the author. However, what is true for marble is equally so in principle for many industrial minerals. The problems of any stone industry are to maintain markets, create new outlets for stone already in demand, and develop varied uses for varieties that are not so popular. Here the geologist has a different role from most of his colleagues in metal mining. The producing branch may ask about the expectable variation in thickness or size of a deposit as development proceeds. The stock department may call for the available amount of a given type of stone before accepting a large order. The sales force requires data on the use for stone from certain parts of deposits in order to divert grades to the most suitable use. The service depart-ment wants defects rectified and the cause determined to avoid recurrence. The mills want data on durability and cutting quality of abrasives. The geologist occupies no special department; he is on general call, as may be illustrated by a few types of problems that may be classified as: (1) dominantly geological in character, (2) dominantly chemical in character, (3) dominantly physical in character.

Jan 1, 1940

By W. F. Boericke, T. H. Garnett

The Wisconsin zinc district, or the Upper Mississippi lead and zinc district as it is also termed, lies in the southwestern corner of Wisconsin, and embraces adjacent portions of Illinois and Iowa. It includes Iowa, Grant, and Lafayette counties in Wisconsin, and Jo Davies country in Illinois. In Iowa, Dubuque formerly produced considerable lead, but there has been little mining there in recent years. The map, Fig. 1, shows the entire district, withroads, railways, streams, and the various towns, or "camps," around which the mines are clustered. The hatchwork indicates the areas in which lead and zinc have been mined. The district is about 60 mi. (96 km.) north and south and about 40 mi. (64 km.) east and west. Not all of the territory is mineral bearing, and there are considerable areas that are believed to be barren. The grouping of the mines is patchy and irregular, though certain broad zoncs of mineralization extend almost the full width of the district, as from Mineral Point west through Mifflin and Livingston, and from Shullsburg west through New Diggings and Hazel Green. It is worth noting that the best mines of the district have, to date, been found within 10 mi. ease or west of the fourth principal meridian line, thus lying within a long, narrow, north-and-south belt extending the length of the district. In a field as large as the Wisconsin, which has only within comparatively recent time been worked intensively for zinc, the chances are good for opening new and important orebodies in parts of the district not yet, or insufficiently, prospected. However; the prospecting has been most successful around, or adjacent to, the old lead diggings of nearly a century ago, and the camps that were well known then are still centers of activity. In their order of importance they are: New Diggings, Ben-ton, Mifflin-Livingston, Galena, Linden, Hazel Green, Shullsburg, and Highland. The district is one of the best farming districts in Wisconsin, with deep fertile soil. The farms are large and well improved, and the towns are modern and prosperous. Railroad facilities are good and proximity to Chicago is an asset. Mining is usually done on a leasing system of 10

Jan 1, 1920

By A. H. Heim

A method and apparatus for measuring gas porosities of rocks are described. The apparatus can be assembled from commercially available components. In principle, measurements are made by volume substitution at constant pressure. The maximum error is not more than 0.3 porosity per cent. Typical results are given. INTRODUCTION Determining the porosity of rock samples is one of the most important and yet most varied types of measurement in core analysis. Among the many techniques devised are the so-called "gas porosity" methods. An old and well known example is the Washburn-Bunting method.' The U. S. Bureau of Mines2-' described and later improved the apparatus for a now widely used method generally known as the "Boyle's law" method. In the present form of the Washburn-Bunting method,' the volume of air in the pores of a rock sample at atmospheric pressure is extracted and then collected in a graduated burette at atmospheric pressure. The volume of air is read directly as the pore volume of the sample. The absolute error in reading the collected volume of gas is independent of the total volume; thus, the relative error is larger when the volume is small, as it is for rocks of low porosity. In addition, the sample after measurement contains mercury, which limits its use for other analyses. The Bureau of Mines (or Boyle's law) method measures directly the solids volume of a sample from which the pore volume and porosity are derived, using a separate measurement of the bulk volume. Gas at a few atmospheres pressure is introduced into a sample chamber of known volume containing the rock sample. The pressure is accurately measured. Following, the gas is expanded into a burette at 1 atm, and the gas volume is read directly. From the initial pressure p, and the final pressure p2 and volume v,, the initial gas volume v1 is calculated using Boyle's law; that is, p1v1 = p2v2. Volume v, minus the volume of the empty sample chamber is the solids volume of the sample. The accuracy of the method is limited, unless corrections are made, by deviations of the gas from the "ideal" gas-law behavior assumed in the simple form of Boyle's law. The purpose of the present paper is to describe a method for measuring the gas porosity of a rock which avoids many of these difficulties. Gas volumes are measured directly with the same accuracy as the bulk volumes. Pressures of at least an order of magnitude larger than those of previous methods are employed to insure rapid penetration of the gas into the sample. While special equipment may be built to apply the method, the porosimeter may be constructed as well from commercially available components. For simplicity, the apparatus described will be referred to as the "Constant-Pressure gas porosimeter". THE CONSTANT-PRESSURE METHOD Fig. 1 shows schematically the arrangement of components comprising the present Constant-Pressure porosimeter. Briefly, the method is one of volume substitution and may be considered a null measurement. Omitting (for the present) some of the operational details, the method of measurement consists of the following three steps. 1. After evacuation, the volume of the measuring system (a ballast chamber, a manifold, two gauges and their connections) up to the sample chamber is filled with gas to a high pressure (- 1,000 psi). A sample of the gas at this pressure is trapped in one side of a sensitive differential pressure gauge to serve as the reference pressure for subsequent steps. 2. The evacuated sample chamber containing the rock sample is opened to the measuring system. As the gas expands into the chamber, the resulting decrease in pressure unbalances the differential pressure gauge. 3. The pressure is restored by means of a mercury volumetric pump. The volume of mercury injected exactly equals the free or void volume of the sample chamber (volume of empty chamber minus the solids volume of the rock within). From the injected volume and the known empty chamber volume, the solids volume is obtained and the porosity calculated. The pressure and the volume occupied by the gas are the same before and after opening the sample chamber. Expansion and compression of the gas are incidental operations and do not enter into the calculation of porosity. By the pressure balancing or nulling, the free volume of the sample chamber is merely substituted by an equal and measured volume of mercury. Since the measurements are at constant pressure, there are no compressibility corrections necessary for the sample chamber.

By Edward W. Parker

This plant was built in 1907 at the Bankhead mines to manufacture briquettes by the Zwoyer process under license from the Zwoyer Fuel Go., of New York, N. Y. The building was constructed to contain two units, each of a capacity of 10 tons per hr.; one unit was installed at the time the building was constructed, and the second unit is now being built. The coal used is an anthracite, which is more friable than that of Pennsylvania, and, as a consequepce, a larger percentage of dust or waste is produced, which was formerly thrown upon the slack-pile as waste, but is now passed to the " dust-bin " in the breaker, from which it is conveyed to the briquette-plant. An average analysis of the coal, published by Lewis Stockett and 13. R. Warden,' is as follows: Per Cent. Moisture,.........0.50 Volatile,..8.00 Fixed carbon,... 83..50 Ash,.......8.00 Total,.100.00 Sulphur,.........0.40 per cent. Specific gravity,...... 1.40 Color of ash,.white Heat value,.......14,000 B.t.u. The plant is run under two 12-hr. shifts, the force consisting of 1 superintendent for both shifts, 1 engineer for each shift, 1 briquetter for each shift, 1 helper for each shift, 1 laborer cleaning up for each shift. In the pitch-melting house, 2 men are on duty for one shift. The steam for the engine is furnished from a central boiler-plant, which also supplies steam for the breaker, the electric light and power-plant, machinery-shop, and boiler-shop. During March, April, May, and half of June, in 1907, the

Jan 1, 1909

By Alfred F. Brainerd

Some fifty years ago, iron-ore was discovered near the town of Sheldon, Franklin County, Vermont, in a vein out-cropping on a knoll near Black Creek, which empties into the Missisquoi River a couple of miles away. A short time after this discovery, the owners, Mr. TV. 0. Gadcomb and Hon. Lawrence Brainerd, both of St. Albans, commenced mining (mostly by open cut), and also erected a Catalan forge, from which iron blooms were produced, most of which were worked into bar-iron and used in the neighborhood of the forge, while some were shipped by Lake Champlain to Troy, Albany and New York. But by reason of the lack of any railroad connections, and an insufficient demand for the blooms, this forge was subsequently abandoned, and the material used in its construction removed to other places. Mr. Keith, of Sheldon, used for many years a mixture of this ore with bog-ore from Swanton, in a charcoal blast-furnace, the product of which he consumed partly in his own foundry, shipping, however, a considerable amount to Troy and New York. Accurate data as to this enterprise are not at hand. The same vein has since been traced for some 20 miles, and some prospecting has been done 011 its outcrops at Berkshire, Enosburg and a few miles east of St. Albans; but the vein being small, only a few car-loads of ore were taken out from these places. The commencement of the St. Albans Iron and Steel Works in 1872, and the erection in 1877 of a ten-ton Siemens open-hearth furnace for the manufacture of steel rails, opened a new use for this ore. The furnace-charge consisted of pig-iron, old mils, steel scrap, and magnetic iron ore, added towards the close of the heat. The ore

Jan 1, 1885

By Ian W. Wark, Keith L. Sutherland

IT has been shown' that in the absence of heavy metal salts, the nature of the alkali used to promote differential flotation-whether caustic soda, lime or sodium carbonate-is unimportant. The hydroxyl ion is the active depressant upon which differentiation depends, and the pH value determines whether a film of collector forms on any given mineral surface. Even when sodium cyanide is used in conjunction with alkalies, it is the pH value and not the nature of the alkali or its concentration that is important, for upon the pH value alone depends the fraction of the added sodium cyanide that is present as cyanide ion, which is the true depressant. When heavy metal salts become dissolved from partly oxidized ores, or are added intentionally as activators, conditions are different, and metallurgists have found that lime and sodium carbonate do not give identical results, even when added in amounts sufficient to produce the same pH value. In the few instances in which we had attempted to confirm this view, we had failed to do so, for, with nothing to guide us, we had inadvertently chosen solutions that gave contact curves of a "standard type," which correspond to conditions of ready floatability. Now, however, we find that, in the presence of copper salts, and within a restricted range of reagent concentrations, the nature of the anions present is important, and that sodium carbonate does influence the results, apart from the usual effect due to its influence on pH value. With the recognition of this anion effect, and with the control of temperature already introduced,2 it appears that the factors of major importance in connection with this set of reagents have been taken into consideration, and that the results obtained and the conclusions drawn from contact tests will be of more immediate value to the operator. It is not difficult to suggest an explanation for the influence of the carbonate ion in the presence of copper sulphate. The works of Picker-

Jan 1, 1939

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By F. V. Lenel

R. P. Seelig.*—Dr. Lenel is to be congratulated on his presentation of a particularly interesting paper describing the use of the powder metallurgy process for the production of magnetic pole pieces. The only thing that might be added is that we have been successful in producing pole . pieces with a narrow hysteresis curve by the use of considerably lower sintering temperatures than the ones used by Dr. Lenel. It is quite possible that this use of lowe- temperatures has considerably widened the field of commercial application for pole pieces made from metal powders. Development work is currently being done on an a.c. application of a sintered iron part. However, I am in full agreement with Dr. Lenel that if eddy currents are an important factor in the application, we cannot substitute sintered material for laminated sheet-metal structures. Mr. Peters' remarks concerning the limitations of machine parts were well taken. The emphasis of the limitations makes it easier to define clearly what we can do and-what the advantages are of machine parts made of metal powders. When I mention metal-powder machine parts, I mean those of relatively high density, although complete elimination of porosity is not possible at this time. The limitations of the field for this type of parts are largely economical. I believe that Mr. Langhammer has made that point very clear. The following questions are very often asked: How large a part can you make? How close can you hold the dimensions ? How fast can a part be produced? In a majority of the cases, it depends on the cost at which the part can be produced. A large variety of shapes and sizes of a number of materials can be formed. However, the main requirement in this field of endeavor is whether this can be done more economically by powder metallurgy than by other manufacturing methods. As a general indication, it may be stated that densities up to 95 per cent of that of rolled material can now be produced commercially in simpler parts. Tolerances of plus or minus 0.001 in. are common, but where special conditions justify, closer tolerances can be held; we are producing a part of which one dimension is held to 0.0003 inch. Finally, as far as maximum size is concerned, technically this would depend on the capacity of the press and furnace equipment available. Actually, we find that the economical limit of powder-metallurgy machine parts is approximately one pound. From there on, each individual case must he studied on its own merits.

Jan 1, 1945