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By J. Szekely, J. W. Evans

A formulation is given for radiant heat loss from the surface of molten steel held in a ladle and numerical solutions are presented for the resultant integrodif-ferential equations. The results are shown on plots of the net rate of heat loss against time, with the geometlry, emissivities, thermal properties of the walls, and Preheat as parameters. It was found that the rate of the vadiant heat loss from the exposed metal surface was comparable to the conductive losses from the Portion of the metal in direct contact with the walls. The radiant heat loss was markedly affected by the geometry and by the thermal properties of the walls the net radiant heat loss from the steel could be drastically reduced by providing a top cover and also by the provision of preheat. The results of this work are thought to be relevant to heat loss calculatious concerned with vacuum degassing and with operatzons in which molten metals are held in ladles. WhEN molten steel is held or transferred in ladles heat losses inevitably occur. The accurate assessment of these heat losses is of importance in process design considerations, as the temperature of the metal may have to meet rigid specifications in certain stages of the processing sequence. As shown in Fig. 1, the principal mechanisms responsible for heat loss are: i) Conduction into the walls and ii) Thermal radation from the top metal surface (possibly augmented by natural convection) The conductive heat loss may be readily calculated as much information is available in the literature on both the general theory1'' and on its particular applications to ladle heat loss calculations. Evaluation of the radiant component of the heat loss is less straight-forward. In two recent papers it has been shown that the presence of a slag layer 2 to 3 in. thick would prevent any significant heat loss for periods up to an hour,5'" however, should bare metal be exposed, constituting the radiant surface, substantial heat losses could occur. This latter case is of considerable practical interest in various degassing operations and in the vacuum processing of certain specialty steels, where the top surface of the metal is not covered by a protective slag layer. Under these conditions a substantial radiant flux is emitted by the top metal surface; part of this flux leaves the system, part of it falls in the ladle walls. The radiant flux incident on the ladle walls is in part absorbed and conducted away, and in part reflected and re radiated. The purpose of the paper is to present a general formulation of the problem, the resultant solution of which should enable computation of the net radiant heat loss from the metal surface. The principal variables, the effect of which will be investigated, include initial metal temperature, geometry, thermal and radiative properties of the wall, and various modes of preheat. FORMULATION Consider a cylindrical enclosure, shown in Fig. 2, with a diameter D, height H, and wall thickness W, the cover at the top of the cylinder having a wall thickness L. If the temperature of the base (representing the top surface of the metal) is kept constant, say, Tb, the problem is to calculate the net rate of heat loss from the base as a function of time, geometry, the initial temperature distribution, and the thermal properties of the system. As customary, the formulation will consist of the mathematical statement of the conservation of thermal energy within the system.

Jan 1, 1970

By R. E. Lund

Josephtown Smelter employs the St. Joe-developed electrothermic process for producing zinc metal and zinc oxide. The process uses resistance-type electric furnaces. Flow of current through the sintered ore and coke charge develops the energy required for smelting at the reaction sites. To produce zinc metal, the furnace off-Gases bubble through a large "U"-tube filled with molten zinc which condenses the zinc to liquid; the metal is then mechanically cast into slabs. To produce zinc oxide, the furnace vapors burn in air and the resultant powders are collected. The smelter comprises three distinct circuits. One circuit produces American Process zinc oxide and high grade metal; another circuit produces tailor-made alloys of controlled lead and cadmium content; the third circuit produces prime western zinc metal and feedstock which is refined into special High grade metal and French Process zinc oxide. The roasting circuit utilizes multiple-hearth furnaces for deleading the zinc concentrates; fluid bed and suspension roasters are employed for desulfurization. Sintering produces a hard, porous furnace feed. The flexible smelting process is adaptable to consuming various kinds of secondary material. Extensive residue treatment accomplishes high overall zinc recovery. Smelter by-products include sulfuric acid, cadmium, and mercury.

Jan 1, 1970

By Robert L. Marovelli

A recent reorganization placed the health and safety research activities of the Bureau of Mines under a director, Division of Minerals Health and Safety Technology. The new health and safety research organization and its position in the Bureau hierarchy is shown in Table 1.

Jan 11, 1979

By T. R. Scott

The acid pressure leaching of zinc-lead flotation concentrates from the McArthur River deposit, Northern Territory, Australia, has been studied in a three-stage, continuous, co-current system, using titanium reactors of 6 gal capacity. The starting pulp contained 2.7 lb solids per gal of synthetic spent electrolyte and the final liquors contained 120-125 gpl Zn. Parameters investigated included temperature (95-120°C), oxygen pressure (30-100 psi), acid addition (80-130% of theoretical), and leaching time (35-65 min per stage). Technical factors studied included mixing and pumping of feed, agitation, settling and washing and control mechanisms. The chemistry of liquor impurities, of scale formation in autoclaves and of lead jarosites in residues was studied in some detail. Results indicated that 90-93% zinc recovery could be obtained with a "low- acid" process, using 113°C and 70 psig with oxygen as the favored operating conditions. Residues contained 16-18% elemental sulphur and 15% lead, together with unreacted pyrite and gangue minerals. Pelletizing of residues was impracticable, and alternative suggestions for the recovery of lead, sulphur and silver are discussed. Preliminary estimates for plant and operating costs are given and enable some comparison to be made with conventional procedures.

Jan 1, 1973

By Henry D. Hibbard

FoR the purpose of this paper all steels will be divided into two divisions: effervescing and non-effervescing. This classification must be borne in mind as many statements true of one class are not true of the other. Effervescing steels are those that effervesce in the molds, evolving large volumes of gases, which, in escaping, throw up a spray of molten particles of steel and give the molten metal in the mold a rapid stirring or churning motion until it freezes, or, at least, becomes pasty. This effervescing is intended and proper. The non-effervescing steels, which are more or less completely killed, should not evolve any gas in the molds. Many years ago the writer proposed to call the two classes of steels evolution and solution steels, depending on whether the gases in the molds are evolved or kept in solution, but the present designations seem to be better. In America, at least, effervescing steels are in a class by themselves and include steels made for boiler, tank, and ship plates, steel pipe, soft steel wire, wire nails, soft machincry, and structural steels. These are all low-carbon steels with less than 0.40 per cent. carbon. Low-carbon steels that do not effervesce but are killed are also made; these are put into ingots and castings but they are outside the limits of this paper. Effervescing steel is cast into square or slab molds, either top or bottom poured. Most of the effervescing steel is made in the basic open-hearth furnace, though much is made by the acid Bessemer process and a little is made in the acid open-hearth. It is not made by the crucible or electric-furnace process, in which the volume of gas required cannot be produced in the steel and evolved from it in the mold to give the effervescence desired. Any steel ingot, when teeming is finished, is of a certain size or volume. Leaving out of consideration for the moment the lessening of the over-all dimensions of the ingot through contraction due to loss of heat, the ingot may be placed in one of three classes: It may settle, losing in volume; it may stand, that is, remain constant in volume; it may rise, that is, increase in volume. Into which class an ingot will fall depends on the gases of the steel,

Jan 1, 1920

By R. M. Brick

Segregation can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-I2 per cent Si alloys. The phasial condition implicitly described above—solidification over a range of temperatures with a compositional difference between solid and liquid—is found in nearly all solid solutions or combinations of solid solutions and eutec-tics, Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually deter-minable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be described first because it is an essential part of the picture. Coring Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus I, 3, 7 and solidus 2, 5, 8, and where the vertical I, 4: 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. Ib) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1945

By J. P. Carson

THE Croton water-shed furnishes the source and storage of watersupply to both the old and the new aqueduct. The Croton river rises in the southern part of Dutchess county, about 68 miles from the lower end of New York city. Its three main branches, called the East, Middle and West branches, flow southward across Putnam county, joining, near its southern boundary, to form the Croton, which continues thence in a general southwest direction across Westchester county to the Hudson river at Croton Point, about 35 miles north of the city. The water-shed above the proposed site of the Quaker Bridge dam extends about 33 miles north and south, with an average width of 11 miles, making in all about 362 square miles, from which, by complete storage, an average daily supply of 250,000,000 gallons may be collected—sufficient for the needs of the city, probably, for the next fifteen years. The water-shed above the Croton dam is 23 square miles smaller, and furnishes the present daily supply of 100,000,000 gallons. By referring to the map it will be seen that the shortest approximately straight line between the proposed site of Quaker Bridge

Jan 1, 1891

By T. A. Rickard

RICO, in the southwestern corner of Colorado, is one of the productive mining centers of the San Juan region, so-called because its waters drain into the river of that name, which is tributary to the Colorado. The San Juan region includes the counties of Ouray, Hinsdale, San Miguel, Dolores, San Juan and Montezuma. It is traversed by a network of picturesque mountain ranges on whose lofty summits there rests perpetual snow. The region is peculiarly rugged, and, in the early days of its development, tested to the full the hardihood of the adventurers who first explored its can ions 111 search for gold and silver. A prospecting party, guided by Jim Baker, scout and trapper, penetrated in 1861 this part of the territory of Kansas. At that time the country was in the possession of the Ute Indians. In October, 1873, by the Brunot treaty, they ceded to the United States Government the richest mineral-bearing portion of their

Jan 1, 1897

By R. H. Landshof, Reynold Q. Shotts, James A. Redding

GENERAL INTRODUCTION by R. Q. Shotts The sizing of coal particles is one of the most important beneficiation operations performed from the time coal is broken at the face until it is delivered to the customer. Indeed, in many cases it may be virtually the only such operation performed in that interval, although it is most often accompanied by some comminution. Sizing, as the term implies, is a separation of the broken coal particles into arbitrary groups, each group containing particles within restricted mass, volume or size limits. Size itself is not a rigidly defined property, but is actually determined more by the operating principles of the sizing device than by unique properties of the particles themselves. Particle size cannot be uniquely defined independently of particle shape. Taggart l says, "In fact, it is not possible to state the size of a single irregular body by means of a single dimension; such possibility exists only for regular polyhedra and their limit, the sphere." In view of the scarcity of regular polyhedra among coal particles, even though most appear to approximate a cube, we actually define size in terms of a surface opening through which the particle barely will or will not pass, or of two openings, the smaller of which retains all particles of the group under study and the larger of which passes all of them. Alternatively, size is expressed in terms of rate of settling of particles in a fluid under closely controlled conditions. Historical Sketch2-Taken from Coal Preparation, 2nd Ed. "Sizing is the process of separating mixed particles into groups of particles all of the same size or into groups in which all particles range between certain definite maximum and minimum sizes. In coal preparation, sizing is generally accomplished by passing the coal over screens. Separation by differential settling in air or water currents has been adapted to the special field of separating very fine sizes, and these processes are in commercial use to a relatively small extent in the coal industry. Separation with screens is a very old industrial practice. Agricola described the use of screens for ore treatment in the middle ages. In the literature of the British coal industry references were made to the screening of coal as early as 1589, but the practice of extensive sizing for the market did not become general until the last half of the nineteenth century. "In America, the practice of sizing developed first in the Pennsylvania anthracite region, beginning with the use of rakes in the mine working places to recover coarse coal. The mining procedure left the fines in the mine.

Jan 1, 1968

By M. R. Geer Olds, H. F. Yancey

THE increase in the number of coal-cleaning plants employing dense-medium processes occurring since 1946 is especially interesting when viewed historically. Both sand and magnetite were introduced as material for heavy mediums at about the same time, sand in the Chance process in 1921 and magnetite in the Conklin process in 1922, but from that point on their records diverge. The Chance process enjoyed a steady growth from its inception, whereas no additional magnetite plants were built in the United States for over 20 years. Then, following the close of the World War 11, magnetite was again introduced, this time with marked success. During the following years some 47 plants employing magnetite medium were built. This rapid growth of dense-medium cleaning has been concurrent with widespread adoption of full-seam mining on one hand and a return to a more competitive market on the other. At a time when changing mining practice has provided cleaning plants with dirtier coal and changing market conditions have simultaneously demanded a cleaner product, the industry has through necessity turned to improved preparation. The inherently greater sharpness with which dense-medium processes can separate coal from impurity is thus helping to hold the line against ever-increasing mining costs and at the same time assisting materially in retaining badly needed markets. Although dense-medium cleaning unquestionably offers a distinct advantage when the washing problem is difficult, other methods can provide almost equally high efficiency when the coal is easy to wash. Moreover, fine coal cannot yet be treated by heavy medium in a proved process, although the Driessen cyclone is in the pilot-plant stage. Most of the present types of dense-medium equipment have been in use only a few years, and the dearth of information in the literature concerning their performance characteristics is entirely understandable, Nevertheless this information is necessary if the process is to be intelligently applied to individual cleaning problems. Without data on the efficiency of a process in a particular type of separation, it is difficult to assess the advantage to be expected from it. Similarly, the role of particle size in heavy-medium separation is important in some cases, yet there is little published information on this aspect. To mention only one more of the numerous points on which essential information is lacking, the bearing of medium characteristics on performance has been discussed only in qualitative terms. It was with the hope of providing information on some of these points that the Bureau of Mines built a dense-medium pilot plant for cleaning coal at its Northwest Experiment Station in Seattle in 1950. The plant has been operated continuously since that time, and over 50 runs have been made on 7 coals exhibiting a wide range of washability characteristics. An idea of the magnitude of this work will be gained from the fact that examination of the plant products has involved some 600 float-and-sink separations and about 2500 ash determinations. A laboratory pilot plant is especially well adapted to investigate many aspects of performance because close control over test conditions can be exercised and because a large number of tests can be made rapidly. On the other hand, factors such as consumption of medium and other cost items can be investigated satisfactorily only in a commercial plant. Actually, the two forms of investigation should be complementary, with the laboratory work pointing the way for confirming tests in commercial units. Pilot Plant The dense-medium pilot plant employed for this work comprises a 24x30-in. drum-type separating vessel, a 12-in. densifier, a 12-in. magnetic separator, a 26-in. x 9-ft vibrating screen, and the necessary pumps and conveyors for handling materials. Arrangement of these units corresponds with the flowsheet used in most commercial plants, except that a thickener is not provided for the feed to the magnetic separator. Coal and refuse discharge from the separating drum to the vibrator, which is divided longitudinally down the center. Medium draining through the first 3 ft of the screen is recirculated directly to the drum. Sprays on the middle 3 ft of the screen rinse medium from the products, and the last 3-ft section is for dewatering. Dilute medium from the rinsing and dewatering sections is pumped to the magnetic separator, where magnetic solids are recovered. These are pumped to the densifier, from which they return to the medium-drainage sump by gravity through a demagnetizing coil. The drum-type separating vessel is a scale model of a commercial unit. Feed enters axially at one end of the drum just below the surface of the bath, and float material overflows through a circular opening at the other end. Particles sinking to the bottom of the bath are picked up by lifting flights bolted to the inner wall of the drum, elevated out of the bath, and sluiced to the vibrating screen. Baffles suspended in the bath prevent float material from entering the sink-lifting flights. About 8 gpm of medium is used to sluice the feed into the drum. An additional 15 to 24 gpm, depending upon operating conditions, is added through two pipes dipping into the bath behind the baffle on the side where the sink-lifting flights enter the bath. The bath available for separation is 2 ft long and 13 in. wide, giving an area of 2.08 sq ft. Depth of bath from the surface to the top of the sink-lifting flights, measured vertically below the axis, is 6 in.

Jan 1, 1954

By Philip D. Shelton

INTRODUCTION Traditional design of support for permanent underground mine excavations place great emphasis on the magnitude of the maximum radial load which a specific support or lining must sustain. However, this depends upon so many factors that reliable prediction in advance of excavation is very difficult except in strong-self supporting ground. Some of the factors affecting the loads acting on a support are illustrated in Table 1. [ ]

Jan 1, 1984

By Robert Mehl

METALLURGISTS are properly interested in papers dealing with subjects ranging from the theories of the metallic state to very practical details on the use of metals. A review of theoretical metallurgy naturally excludes papers concerned with the usefulness of metals and limits itself to those concerned purely with the science of metals. Even in this more limited field the reviewer is confronted with thousands of papers dealing with facts and theories of metallic behavior, from which he can select only a few hundred. The selection is necessarily highly arbitrary. Certain classes of papers definitely fall within the scope of this review. Thus, papers on the deformation of metals, on the structure of alloys, on recrystallization, to select only a few, are fully represented. Other subjects, which verge on what is generally accepted as the science of metals, such as the magnetic properties of metals, the less familiar electrical properties and theories, adsorption of gases by metal surfaces, and the like, are treated scantily. Particular attention is given to reviews of subjects that fall with in the groups chosen; in a summary such as this, which is largely in the nature of a progress report, capably written reviews are of importance, particularly since the monograph and text book literature is so meager in this field.

Jan 1, 1935

By K. E. Gray

The status of rock mechanics as applied to petroleum production might be termed, "Rock Mechanics-A New Name for Old Problems." The petroleum industry's efforts, from its earliest days, have been concerned with rocks, hopefully containing hydrocarbon accumulations in economic quantities. Geophysical and geological studies, wildcat and development drilling procedures, well bore mechanics and reservoir engineering operations, and certain aspects of production operations involve rock mechanics in various ways. Stress states and temperatures of interest range from low values in surface or near-surface activities, to very high values encountered at depths now exceeding 25,000 ft; deeper and deeper drilling will continue to increase this range. Time scales vary from a few microseconds in wave propagation measurements and some aspects of rock behavior during drilling, to seconds, minutes or hours for other drilling and well bore mechanics problems, to several years during which the efficient and economical depletion of reservoir systems is achieved. Subsurface sedimentary formations contain various fluids, of course, and reservoir fluid movement commonly involves three-dimensional, three-phase (oil, gas, and water) fluid flow. Many extremely difficult problems in rock mechanics arise for the Petroleum Engineer because of fluid movement (or lack of desired movement) in a well bore or reservoir. The discussion to follow illustrates just a few of the many topics in rock mechanics of significance to the petroleum industry. Time precludes anything other than a superficial treatment of the topics mentioned. A great deal of work has been carried out by various research groups in the petroleum field and significant efforts are continuing, as a review of the technical literature will reveal.

Jan 1, 1968

By G. C. Fryburg, H. M. Murphy

ThE rates of oxidation of metals are usually obtained by heating the metal specimens in furnaces. Such a procedure is satisfactory for most metals. However, there are several metals that oxidize according to the reaction.

Jan 1, 1959

By M. C. Lavine, H. C. Gatos, R. S. Mroczkowski

The structure of GaAs-Ge heterojunctions prepared by a back-melting process was studied by X-rav diffraction, melallographic, and electron-micro-analyzer techniques. The boundary region between the GaAs and the germanium was found to consist of a four-layered band. A discontinuity between the two inner bands was brought about by solidification occurring simultaneously from the GaAs and the germanium side. The junction material OH either side of the central discotinuity was found to have grown as a single Crystal with the orientation of the parent substrate. It was found essential to determine the GaAs-Ge phase diagram. This was accomplished by a series of alloys containing 0 to 40 wt pet GaAs. Over this range the diagram is a simple eutectic with the eutectic point at 74 wt pet Ge and 845 C. The limiting- solubility of Coils in germanium was found to bc less than 5 wt pet. The Kossel divergent-beam X-ray technique was used to study orientation relationships across the boundary lager. A great deal of effort has been recently expended on the electrical properties of heterojunctions. Little attention, however, has been given to the metallurgical variables which may be of importance in the formation of the junctions. The present work was undertaken to investigate some of the more pertinent metallurgical aspects of interface-alloyed GaAs-Ge heterojunctions. Such parameters as solidification processes, composition gradients, orientation effects, and the accommodation of crystal structures have been the objects of study in this program. EXPERIMENTAL PROCEDURES Phase Diagram. The phase diagram of the GaAs-Ge pseudobinary system was determined by means of cooling curves. A Bridgeman furnace was employed with the center section maintained at 1200°C and the upper section at 800°C. Melts varying from 0 to 40 at. pct in GaAs content were used. Each charge was incapsulated under a two-thirds atmosphere of argon in a carbon-coated quartz tube. Five min in the furnace hot zone provided rapid melting and homogenization. The capsule was then removed to the cooler portion of the furnace. Cooling times were of the order of 3 min. The resulting homogeneous microstructure indicated that equilibrium conditions were obtained by this procedure. Formation of Heterojunctions. Rectangular parallelepiped single-crystal samples were cut with the large faces of either the (l00), (110), or (111) orientation. The remaining four surfaces were also cut to specific orientations to permit accurate relative orientation of the GaAs-Ge pairs. The

Jan 1, 1965

By H. F. Moore

Jan 1, 1936

By H. F. Moore

Jan 1, 1936

By Albert J. Phillips

IT is a privilege and a pleasure to deliver this, the Twenty-sixth Annual Institute of Metals Division Lecture. Eleven years ago C. A. Edwards addressed this audience on the subject "Gases in Metals." In spite of this relatively recent presentation, I propose to, present to you some quantitative considerations of industrial significance on the separation of gases from molten metals because recent observations and measurements, presented in the literature, have made it possible to evaluate mathematically the gases or gas-forming elements and to develop an understanding of the mechanism of gas separation that should permit, in many cases, the control of this baffling phenomenon. DEFINITIONS Before becoming involved in the subject it seems desirable, for the sake of clarity, to state certain definitions and axioms: I. We are dealing only with gases that separate from the molten metal either during cooling or in the transition from liquid to solid. Gases injected by the liquid stream and trapped in the solidified metal, or those forced into the solidifying metal from the mold due to either thermal or cher4ical effects are not considered. Neither are we concerned with the separation of gases within the metal after solidification is complete for the data on this subject are at least complete enough to permit the practicing metallurgist to satisfactorily control the phenomenon. 2. Only where there is a decrease in solubility or a change in equilibrium of either a gaseous element or an element that reacts to form a gaseous compound, can there be a separation of a gaseous phase from the liquid or solidifying metal. 3. The amount of gas separating from the liquid during solidification can be computed directly from the amount of the element contained in the liquid when freezing commences less the amount of the element found in the solid either as a separate solid phase or in solid solution. 4. There can be no separation of gas bubbles unless the told pressure of the gases in the liquid meld exceeds atmospheric pressure plus the hydrostatic pressure of ' the liquid metal head. (In addition, pres- sure resulting from surface tension in- creases the total pressure requirement for initial gas separation. Probably the remarkable differences in appearance caused by different gases in the same host metal are influenced greatly by the rate of diffusion of the gas in the liquid metal balancing the decrease in pressure as the gas bubble size increases and the surface tension effect decreases. Thus hydrogen with its high diffusion rate in liquid copper separates in the form of relatively coarse cavities for a given rate of heat extraction.) 5. Gas separation can take place at less than atmospheric pressure in the voids created by the shrinkage from liquid to solid, but since the voids are not caused by the gas the presence of gas in the voids is of importance only where it

Jan 1, 1947

By H. Hubert

The first attempts at direct utilization of blast-furnace gas in engines were made in 1895. For a considerable time the gas had been burnt in Cowper stoves for heating the blast for the furnace, and under the boilers which supplied steam to the blowing-engines, and others serving the furnaces. It was natural, therefore, that the idea of directly employing it in gas-engines should have occurred simultaneously to several engineers, notably to Lurmann and to Lencauchez, who had pointed out the blast-furnace as a powerful gas-producer. Nevertheless, nowhere had any attempt been made to apply it to this purpose up to the end of 1894, when Thwaite proposed it to Mr. James Riley, of the Glasgom Iron & Steel Company. About the same time investigations were being made in Belgium and in Germany, independently of Thwaite's experiments, which were not generally known on the Continent. The industrial world, which up to that time had hardly favored the idea, had thus been gradually prepared to receive it. The gas-engine, long restricted to small sizes and dependent upon the use of an expensive fuel obtainable only in large centers, now began to make headway. At the Paris Exhibition of 1889 two engines of 100 h.p. were shown and excited much interest among engineers. One had four cylinders, and was made at the celebrated works of the Deutz Company, and the other was a single-cylinder engine, exhibited by two French designers, Messrs. Delamare-Deboutteville and Malandin. In the meanwhile the design of gas-producers had made important progress, completely freeing the new engine from its

Jan 1, 1907

By K. A. Svanstrom, W. R. Opie

Problems associated with deposition of titanium infused chloride baths using TiCl4 as a feed material are reviewed. A potentially workable cell design using Alumdum diaphragms is discussed. Problems inherent to diaphragm-type cells are emphasized and experiments described which led to the development of a cell without a diaphragm. INVESTIGATORS assigned the problem of developing a commercial electrolytic process for making titanium metal have found that they are faced with the difficulty of overtaking rapidly improving magnesium and -sodium reduction processes. The ultimate goal must be a simple process that can be conducted with low-cost raw materials in equipment that is inexpensive to build and operate. This paper deals with some work of a preliminary nature conducted by personnel of the Research Laboratories, National Lead Co., Titanium Division. Many others have reported on the general subject of depositing titanium from fused salt electrolytes. A partial bibliography is attached. PRIMARY CONCEPTS Anyone attempting to deposit titanium metal from fused chloride electrolytes using TiC14 as a source material is faced with at least the following problems: 1) Getting the titanium into solution in the bath. 2) Controlling oxidation and reduction reactions associated with multiple valency of titanium, which result in low electrical efficiency. a) Prevention of dichloride oxidizing to trichloride and trichloride to tetrachloride at the anode. b) Prevention of trichloride from being reduced only to dichloride at the cathode. 3) Prevention of metal formation away from the cathode thru disproportionation of titanium dichloride to satisfy the equilibrium. 3 TiCl2 == 2 TiCl3 Ti [I] 4) Protection of reduced chlorides in the bath from reaction with oxygen from the bath container or air. 5) Removing from the bath the deposited metal formed without allowing it to become contaminated with oxygen or nitrogen. 6) Selecting cell materials of construction which will not contaminate the metal product or cause cell inefficiencies. EARLY EXPERIMENTS The initial attempts made to electrodeposit titanium from fused chloride baths using TiCl4 as a source material indicated that TiCl4 was essentially insoluble in molten chlorides of alkali and alkaline earth metals. If, however, the TiCl4 was introduced close to a nickel cathode some metal could be formed and appreciable quantities of reduced chlorides would be present. These reduced chlorides reacted with any oxygen present in the atmosphere above the bath and would also diffuse quickly to the anode (graphite) where they would react with chlorine and be evolved as TiCl4. The net electrolytic efficiency of such a cell is essentially nil. The TiCl4 evolves from the anode at almost the same rate that it is introduced in the vicinity of the cathode although a small amount of titanium metal can be formed on the walls of the cathodic pipe. It becomes apparent from the operation of such a cell that: metal can be deposited on the cathode, although of small particle size and a nonadherent nature, and when reduced chlorides are present in the electrolyte, TiCl4 can be absorbed, probably by the following reactions: TiCl4 + TiC12 - 2 TiCl3 [21 2 TiCl3 + 2 faradays - 2 TiC12 + C12 [31 DIAPHRAGM CELLS These facts encouraged the development of cells containing diaphragms to prevent migration of reduced chlorides from the cathode area to the anode. Small-scale cells for process development are described by Alpert, Schultz, and Sullivan.20 A larger brick-lined cell incorporating internal heating by passing ac through the bath is shown in

Jan 1, 1960