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By J. B. Clemmer, P. E. Churchward, C. Rampacek

A cyclic method for processing manganese ores using sodium sulphate as the basic reagent is described. Sodium sulphate is electrolyzed in a diaphragm cell to give an anolyte-containing agentisdescribed.Sodiumsulphuric acid and a catholyte-containing iselectrolyzedincaustic soda, a part of which is carbonated in a cyclic manner to form soda ash. The reduced ore is leached with the anolyte to dissolve the manganese and the impurities are precipitated by addition of catholyte. Manganese in the pregnant todissolvethemanganeseandtheimpuritiessolution is precipitated as synthetic rhodochrosite with a carbonated catholyte, and sodium sulphate is regenerated. Calcining the manganese carbonate gives a high grade product and the carbon dioxide is returned to the carbonation step. The results of laboratory tests using cells equipped with synthetic-fiber diaphragms and permselective membranes, which permit transfer of anions or cations during electrolysis, are described. A METHOD which has been considered for pro-cessing manganese ores under emergency conditions to recover a product suitable for smelting to ferromanganese involves reductive roasting of the ore for leaching with dilute sulphuric acid followed by precipitation of the manganese from the purified pregnant solution with sodium carbonate. Although the process is operable and involves no novel or untried steps, it is noncyclic in regard to reagents. Research seemed warranted to determine if a cyclic process could be developed by electrolyzing the sodium sulphate formed during precipitation of the manganese with soda ash to regenerate sulphuric acid and sodium hydroxide. Reduced ore would be leached with acid anolyte to dissolve the manganese. The iron, alumina, and other dissolved impurities would be precipitated with the caustic catholyte, and the manganese in the purified pregnant solution would be precipitated as artificial rhodochrosite with carbonated catholyte to regenerate simultaneously sodium sulphate for electrolysis. Waste boiler gas and CO, from calcining the manganese precipitate would be recycled for carbonation of the caustic catholyte. There is a surprising lack of data in the technical literature on diaphragm electrolysis of sodium sulphate. One of the more comprehensive papers, by Atwell and Fuwa, describes the problem involved in electrolyzing byproduct sodium sulphate from the viscose process with particular regard to the design and operation of asbestos diaphragm cells. Frisk' also investigated electrolysis of sodium sulphate from viscose-spinning baths to recover caustic soda and sulphuric acid. The objective in these investigations was to produce, by electrolysis and evaporation, a concentrated caustic-soda solution and a sulphuric-acid solution low in sodium sulphate. Because of these requirements, the process was not too attractive despite a favorable yield of caustic and acid with a reasonable power consumption. Because strong acid and base are not required for processing manganese ores and nonelectrolyzed sodium sulphate is not objectionable in either reagent, the present problem was somewhat simpler than that of these investigators. The purpose of this report is to summarize briefly the results of laboratory electrolysis of commercial sodium sulphate in diaphragm cells of different types and the application of the acid and caustic for processing manganese ores in a cyclic manner. Electrolysis in Permeable Diaphragm Cells The principal problem in electrolyzing sodium sulphate in a permeable diaphragm cell is to prevent mixing of the acid and base formed in the anode and cathode compartments. It is not enough to separate the anolyte and catholyte by a single diaphragm. A three-compartment cell in which the sodium-sulphate solution is fed to the center compartment and flows through the permeable diaphragms to the anode and cathode compartments is more efficient electrically. Diaphragms should be porous enough to allow flow of solution to outer compartments but tight enough to prevent gross mixing of the anolyte and catholyte. In addition to being resistant to acid and alkali, the diaphragms should offer minimum resistance to the flow of current. It is also important that the electrolyte contain a high concentration of sodium sulphate to furnish an abundance of sodium and sulphate ions and thereby decrease the current carried by hydrogen and hydroxyl ions. A practical limitation of sodium-sulphate concentration is imposed by the decreased solubility of sodium sulphate with decreasing temperature. At 20°C, a concentration of 200 g per liter sodium sulphate can be maintained. Little is gained in conductivity by using a concentration greater than 200 g per liter. The small-scale continuous electrolysis tests were made in a 12x12 in. open-top bakelite cell equipped

Jan 1, 1956

By Alexander L. Holley

Jan 1, 1879

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Jan 1, 1961

By Jerome Alexander

The object of this paper is to show that many of the important phenomena of metals and alloys are due to the facts that, at some stage, metals and alloys, or some of their constituents, are in a colloidal state and that a portion of the metal or alloy tends to remain in this state. The so-called amorphous phase in pure metals is an isocolloid, consisting of colloidal groups of metal molecules that may be dispersed in still more finely subdivided metal; these colloidal particles are not truly amorphous, but may consist, in part, if not entirely, of ultramicroscopic crystals; as a result the expressions amorphous phase and amorphous theory might he replaced by the expressions colloidal phase and colloidal theory. Any substance is in the colloidal state when the constituent particles consist of molecular or atomic groups, whose size varies approximately from about 100 down to about 5pp, that is from just below the limit of microscopic resolvability to the dimensions commonly ascribed to the larger molecules. Colloidality involves no assumption as to the shape, internal structure, or orientation of the colloidal particles; size alone is the critical factor. A colloidal system may therefore contain crystalline groups, or amorphous groups (non-crystalline, random or haphazard clusters), or a mixture of the two. All colloids consist of at least two phases, the subdivided substance, or dispersed phase, and the substance into which this is subdivided, the dispersion medium. It is not necessary that there be any chemical difference between the dispersed phase and the dispersion medium. As molecular forces are extremely powerful, their application may produce marked changes in the physical properties of metals. It is doubtful whether metal in the interior, especially of large masses, possesses the same properties as that on or near the surface, which alone is open to inspection.

Jan 1, 1921

By William Crane

OPERATORS of diamond drills have long been familiar with thread-like markings or riflings on cores but apparently have given but little serious thought to the conditions that are responsible for their production. The opinion generally held by those who have observed the phenomena is that the riflings are produced directly or indirectly by vibration, but so far as the writer is aware no systematic attempt has been made to demonstrate the fact. A careful search through the literature on diamond-drilling practice has been rewarded by only one reference to such markings of cores. J. N. Justice1 writes, "Of the peculiarities met with in the core, I will mention only one. The core from the "H" drill, at about 360 ft. came out rifled and pentagonal. The change from the circular to the pentagonal was sudden, and for 9 ft. this structure was maintained, when suddenly it returned to the circular. I have not been able to find any one who can explain the cause of this change of form. The drill men marveled at it and suggested vibration, six-stone bits, and several other hypotheses Which need not be mentioned." The writer became interested in the matter of core riflings some 10 years ago while in the Flat River lead region of Missouri, where many remarkable examples of "rifled" cores were observed and collected. Since that time similar phenomena have been observed in various localities throughout the United States and Canada, and samples have been gotten together illustrating a large number of variations in form. After a careful study had been made of the material at hand it seemed desirable that certain data should be obtained from the experience of others regarding the normal action of diamond drills in forming cores, portions of which are occasionally rifled, before an attempt was made to draw any conclusions as to their cause.

Jan 5, 1916

Jan 1, 1925

By J. L. Gillson

Historically, rock deposits and sand deposits of titanium minerals came into production about the same time, although there may be some argument as to what is meant by production. Beach de- posits of heavy minerals in India (Figs. 1-4) and Brazil (Figs. 5) were worked for monazite about the turn of century, but as there was then no market for titanium minerals, these were thrown away. The rock rutile deposits at Roseland, Va., Fig. 6, were worked to supply rutile for titanium chemicals and for coloring ceramics long before there was a titanium pigment business. The pigment industry started about the middle twenties, both in Europe and the U. S., and almost simultaneously the rock deposits at Ponte Vedra Beach near Jacksonville, Fla., were worked for titanium content. Since those days, production from both types of deposits has continued to grow at a rapid rate; many deposits of both types have been found, and reserves have grown to very large figures. In total tonnage of reserves, there is no doubt that the rock deposits are far ahead of the sand deposits; nevertheless there is a very large tonnage of commercial sands available. It is the quality of titanium mineral in the sand and the relatively lower costs of operating sand deposits that have kept them abreast, at least in annual tonnage produced, with the rock deposits.

Jan 4, 1959

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Jan 1, 1951

By H. W. Hitzrot, R. H. Limons, L. V. Fegan

The testing of a new method for measuring pellet-bed temperatures in the traveling-grate or shaft furnace is presented in this paper. This method, using silver-palladium alloy wires as indicators, overcomes disadvantages existing in the methods based on the use of thermocouples which are costly and time-consuming. The authors have developed and tested a new method for measuring pellet-bed temperatures in the traveling-grate or shaft turnace through the use of silver-palladium alloy wires as indicators. This method overcomes the disadvantages of existing methods, which, based on the use of thermocouples, are generally costly and time-consuming. For example, in the case of the traveling-grate furnace, the installation of an instrumented pellet, together with its attached thermocouples, requires stopping the furnace, with resulting loss of production time. As for temperature measurement in the shaft furnace by the existing method, the movement of the shuttle-car feeder seriously interferes with both the actual insertion and the resulting distribution of continuously fed thermocouples. The authors have overcome these difficulties by using, as temperature indicators, a range of silver-palladium alloy wires that can be easily recovered, after firing at any desired location in a pellet furnace. Silver-palladium wires having specific melting points from 2000°F to 2500°F are enclosed in ceramic capsules. Each capsule is placed in a ni-chrome wire basket filled with a sample of green pellets, the baskets being the means for recovering the capsule after firing. After the encapsulated wires have been exposed to the firing cycle, the alloy wires are examined to determine the maximum temperatures attained by the pellet sample. This method gives accurate, rapid determinations of maximum temperatures attained during pellet induration in either the traveling-grate or shaft furnace The new method has the following advantages over existing methods: 1) it is less expensive; 2) no furnace downtime is required; 3) the testing units can, be made in quantity in advance; 4) measurements can be made in rapid succession at all desired locations; 5) measurements of maximum firing temperatures are more accurate; 6) on the basis of points 4 and 5, the new method gives a more reliable picture of the correlation of pellet quality, petrographic textures and maximum temperatures, thus providing a more effective quality-control tool. A disadvantage of the method is, of course, that the measurements are not continuous and only maximum temperatures are determined. TEST PROGRAM Preparation of Materials: CALIBRATION OF ALLOYS - In the following discussion the term "bead point" (see Fig. 1) refers to the temperature at which each alloy begins to melt and form a bead. Fig. 2 gives the bead point curve for silver-palladium alloys. Before the alloys are used in plant tests, the bead point of each alloy should be determined in the laboratory to verify the alloy compositions. Once a given alloy has been calibrated, it can be

Jan 1, 1965

Jan 1, 1942

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Jan 1, 1938

By G. B. Craig, B. Ramaswami

The temperature and strain rate dependence of the flow stress ratio and the stvain rate dependence qi the flow stress of annealed polycrystalline a zirconiur were determined over the temperature range 30 0" to 1000°K. Some evidence was found for strain aging and discontinuous flow in the temperature ranges 520" to 650°Kand650" to 760°K, respectively. The Cottvell-Stokes relationship was obtained when deformation occurred by twinning as well as slip. The flow stress ratio showed a strong dependence on temperature and strain rate above 800°K. The expevirnental evidence indicated that the rate-controllitzg mechanism for the deformation of a zirconium above 800°K was dislocation climb, and that the deformation was not thermally activated in the range 520" to 800°K. The stacking-fault energy of a zirconium was estimated to be about 250 ergs per sq cm. A knowledge of the temperature and strain rate dependence of the applied stress necessary to deform a crystalline solid is essential for understanding the thermally activated processes occurring during deformation.' Several experimental techniques have been developed for studying these processes.273 One of the techniques is the deter mi nation of the strain rate dependence of the flow stress at constant temperature. In close-packed crystals, it has often been observed that the change in stress due to a change in the strain rate varies linearly with the flow stress, (~1,' This relationship, known as the Cottre ll-Stokes law, is obeyed when deformation occurs by glide alone. However, when deformation occurs by twinning as well as glide, there is disagreement among different investigators on whether the Cottrell-Stokes law is observed. Whereas Thornton et ~1.~find departures from Cottrell-Stokes law when twinning occurs in copper, ~avis~ and sasinski? find that Cottrell-Stokes law is obeyed when deformation occurs by twinning as well as slip in cadmium and magnesium, respectively. One of the main objectives of this study is to determine whether the Cottrell-Stokes law is obeyed when deformation occurs by twinning as well as slip. The second technique that has been used extensively to study the thermally activated deformation of crystals is the determination of the ratio of the flow stresses, at identical dislocation structures and con-

Jan 1, 1968

By Zay Jeffries

Tungsten has the highest melting point of all the known metals, namely 3350 C.; it is one of the hardest of the metals; it has the highest equiaxing or recrystallization temperature after strain hardening, of any pure metal known. It is particularly distinguished because, when composed of small equiaxed grains, it is extremely brittle and fragile at room temperature, and when possessing a fibrous structure it may be ductile and pliable at room temperature. The common ductile metals act in exactly the opposite manner in this respect. The present paper will include a brief note regarding the manufacture of wrought and ductile tungsten. The metallography of wrought and ductile tungsten in the various stages of manufacture will be considered more or less in detail. The general relationships between the properties of tungsten and other metals will also be considered. A discussion will be given explaining why fibrous tungsten is ductile at room temperature, even though past experience with other metals would indicate that it should be brittle. Finally, a brief note regarding some new fundamental metallographic propositions relating to all metals will be given. Manufacture of Wrought and Ductile Tungsten Up to about 10 years ago, it had not been possible to work tungsten mechanically. About the year 1908, Dr. William D. Coolidge, of the General Electrie Go., produced ductile tungsten from what was then supposed to be an inherently brittle metal and which, in fact, was inherently brittle in its normal state, that is, when composed of equiaxed grains. Since that time many products, chief among which are the filaments for electric incandescent lamps, have been made from wrought and ductile tungsten. Tungsten is produced chiefly from the minerals wolframite and scheelite.1-8 The ores may be reduced in many ways. For example, the ore may be fused with alkali carbonates and the fusion dissolved in water; sodium tungstate is formed, which is soluble in water. This

Jan 1, 1919

By Charles T. Van Winkle

Until the advent of the porphyry coppers and the introduction of flotation which soon followed, crushing and grinding for many years proceeded along somewhat stereotyped lines, without important alteration in type of machinery. For the finer crushing and grinding, stamps, rolls, and various patterns of Huntington and Chilean mills were in general use. Ball-mills were in use abroad, but owing to their small capacity and the high cost of screens and steel, they never obtained much footing in the United States. Tube-mills were first introduced into the crushing departments of cyanide plants when it was found that for crushing finer than 30-mesh other types of crushing machinery were not efficient. In order to crush with one pass, these mills were made 18 to 22 ft. (5.5 to 6.7 m.) in length. Pebbles were used as a grinding medium and the mills were lined with either silex blocks or fragments of quartz or flint pebbles set in cement. While the cylindrical tube pebble-mill had been used to some extent in small installations of concentration mills, the first instance of its use on a large scale was at the concentrating plant of the Miami Copper Co., where 8-ft. by 22-in. (2.5-m. by 55.9-cm.) Hardinge mills were tried out against Chileans. The results of these experiments led to the gradual replacement of the Chilean by the Hardinge mill. Robert Franke published an article' describing the work done, comparing the two types of mills. At the same time, according to Franke, a test was run using a 6-ft. (1.8-m.) Hardinge ball-mill as a substitute for rolls for intermediate crushing on 1/2-in. material. According to Franke, this mill was soon discarded, since it was found that to obtain the desired product the mill must be limited in capacity. The Miami Copper Co. made no test with other types of ball- or pebble-mills. Following this example, others installed the conical type; and when the Inspiration Consolidated Copper Co. decided to build a concentrator, it adopted the conical mill. As the requirements for mills would be very large, it purchased manufacturing rights in the State of Arizona from the

Jan 1, 1918

Jan 1, 1954