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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

By F. W. SUTTER

IN order to have ore available on the completion of the beneficiation plant at Clifton and to provide for continuous production while underground development was carried out, it was decided to develop an open-pit through the crest of a long hill in which the ore outcropped, using 40-ft. vertical benches.

Jan 1, 1943

By A. H. Bell

The general principles of the gas-lift will not be described in this paper. Only specific details that have not been fully discussed in previous papers, or results that do not fully coincide with conditions previously described, will be dealt with. The principal points to be emphasized and for which supporting data are furnished are as follows: 1. Gas-lift installations usually have comparatively high efficiencies as compared with standard pumping equipment, when reduced to a basis of barrels produced per horsepower installed. 2. Advantages of high-pressure plants from the standpoint of operating efficiency and for the application of the gas-lift early in the life of flowing wells. 3. Evidence of increased ultimate yield through conservation of gas by the gas-lift. 4. Possibility of development of new equipment to increase efficiency of the gas-lift. 5. Indications of the advantages of repressuring as a means of stabilizing gas-lift wells and as a means of increasing ultimate yields. TyPes of Installation The gas-lift installations of the more important companies in California have been of the central-plant type wherever field conditions would permit. This has resulted in greater flexibility and lower installation costs per well than could be obtained with individual well units. In general discussions of the gas-lift method of production, the installation costs are frequently referred to as being too high for economical operation. If the field conditions are carefully analyzed and the plant designed with the idea of obtaining high operating efficiencies, the installation cost per well can be lowered sufficiently to compare favorably with individual well-pumping units, when the operating advantages are considered. Much greater production per horsepower can be obtained with the gas-lift than is possible with pumping equipment. Table 1 shows the unit sizes and costs of gas-lift installations of three companies in the Los Angeles basin. The cost of walking beams, rods,

Jan 1, 1928

air-lift and equipped with tapered tubing of proper design, we would have a gas input consumption of about 2500 cu. ft. per bbl., which at 3 to 4c. per 1000 cu. ft. would be 7 1/2 to l0c, per bbl., and there would be very infrequent loss of production due to stoppages. It has been demonstrated that with efficient design of air-gas lift, the production of wells can be increased much beyond that obtained with the former type of air-lift employed; also that small wells can be operated by air-lift with tapered tubing at a cost that places this method in competition with beam pumps in many fields. The next step in conservation that the writer expects to have an opportunity to demonstrate is that of restoring the pressure in a pool and producing by air-gas lift all of the oil possible to lift economically. This combined operation is probably the method toward which we shall eventually be working in recovering the maximum quantity of oil from pools where the oil is recovered through bore holes. General Discussion on the Air-gas Lift H. P. Porter, Tulsa, 0kla.—The papers presented at this meeting contain a great amount of valuable information. Wonderful progress has been shown in the development of air and gas-lifts. There has been nearly everything brought out that touches upon the subject. The real point that is lacking is exact knowledge of the velocity with in the flow column which will produce the best effect—that is the thing we must know more about. Velocity in Gas-lift Flow In other lines of industry the matter of velocity of fluids in pipe lines has been well analyzed and there are known laws by which to calculate velocity of flow; for instance, in irrigation work large pumps are designed with intake pipos to employ an intake velocity of 4 ft. per scc. By reduced cross-sect'ion the velocity is increased rapidly as it enters the pump and the discharge rate is at 12 ft. per src., which in turn is reduced in the discharge column to 4 ft. per sec. Crushed coal, grain and granular material is found to be best conveyed by air when a pneumatic conveyor is employed at 100 ft. per sec. As in the design of a pumping plant or a pneumatic conveyor, the velocity at the lower end of the column in the flowing well must be controlled within certain limits for best results. Mr. Griswold, I believe, stated that they had velocity as low as 15 it. per scc. and from that up to 78 ft. per sec. Mr. Pierce and Mr. Lewis showed an ideal flow column showing how the velocity increased as the fluid was carried up the column, hut did not give any figures as to the velocity. It would be well to take that sort of a diagram to establish an ideal velocity at the lower or intake end, and then calculate the velocity from expansion of the gas as it goes up. It may be that the, ideal intake velocity would vary, depending on the depth of the well, the quantity of liquid to be handled or the pressure which it may be desired to hold. The subject is one that might be worth much research.

Jan 1, 1928

By J. B. Caine

THE investigation outlined in this paper was carried on at the plant of the Sawbrook Steel Castings Co., Lockland, Ohio. EFFECT OF TEMPERATURE In the study of the effect of temperature, heats were made with the Sawbrook company's standard practice, using multiple slags, the only difference' being that the heats were tapped at two temperatures; one group between 2960° and 3040°F and the other group between 3200° and 3250°F. Slags were weighed throughout the heat at each slag change and after the heat was poured. Only the significant slag weights, those of the total slag and the finishing slag, have been reported.

Jan 1, 1947

By Edwin Higgins

SINCE the "Days of Forty-nine" California has been the premier gold producing state of the union. The greatest production was recorded in 1.852, during which year the state's placer and lode deposits yielded over 81 millions. This peak was followed by a steady decline to about 12 millions during the years 1888 to 189.3, a period marked by the cessation of gravel mining. After 1893, production increased to a new peak of over 22 million in 1915, thereafter decreasing steadily to something over 13 million in 1923. Today; California's gold production shows a decrease of 84 per cent. as compared with the output of 1852, and a decrease of 41 per cent, as compared with 1915. It is not a difficult matter to find the causes of this more recent decline. In 1916 there began an upward swing in the cost of labor, which represents approximately 60 per cent. of the cost of mining, and in the price of supplies, representing the remaining, 40 per cent. This rise continued until 1922 and since that year there has been no decided tendency either upward or downward. The increase in the cost of mining since 1916 is variously estimated at from 50 to 75 per cent.; the price of gold has remained fixed at $20.67 per oz. This condition resulted in wiping out the profits of the low-grade operations which, in recent years, have constituted California's main source of supply of gold ore. It is now predicted that there will be renewed activity in California- gold mining. What are chances for the materialization of this forecast? A boom or even a revival of gold mining must of necessity be brought about or accompanied by one or more of the following factors: 1. A decrease in the cost of mining. 2. An increase in the price of gold. 3. New capital for development. 4. The discovery of new deposits. 5. The revival of hydraulic mining.

Jan 1, 1925

By C. E. Birchenall, C L. McCabe

IN attempting to extend vapor pressure measurements of the type previously reported by Schadel and Birchenall1 for silver and by Schadel, Derge, and Birchenall' for silver-silicon to other systems, it was observed that the materials melted at indicated temperatures 10" to 15" below their accepted melting points. Further investigation revealed that the thermocouple readings were in error due to appreciable conduction losses along the reference thermocouple wires. If the wire diameter of the reference couple inserted into the Knudsen cell was reduced, the correction for the indicating couple changed in a manner tending to explain the melting behavior. When extrapolated to zero wire diameter from measurements with several reference thermocouples of different wire thickness, the melting point of silver then agreed with the indicated temperature at which silver chips were observed to coalesce into a sphere. Approximately the same calibration was given by observing the melting of small wires of silver or gold in the Knudsen cell connected in series with an ammeter, where the leads into the cell were very fine in order to minimize heat conduction. Unfortunately neither of these methods seemed to yield a sufficiently precise temperature calibration to match the apparent precision of the other aspects of the vapor pressure measurement. It was decided. therefore, to redetermine the vapor pressure of silver in another setup under conditions permitting precise temperature measurement. The vapor pressure of pure silver could then be used as an internal calibration of temperature in the older unit in making runs on alloys. This has been done; the present report is a correction to ref. 1. Experimental Procedure The apparatus, shown in Fig. 1, was very similar to that employed by Harteck,3 except that the orifice sizes were smaller and the residual pressure in the vacuum system was probably much lower. A small, sharp-edged hole, nearly circular in shape, was ground into the rounded end of a quartz tube. The orifice area was then measured by tracing the image at known magnification on graph paper and counting the squares enclosed. The silver specimen was sealed into the tube to make a Knudsen cell. A tantalum jacket surrounding the cell served to increase the uniformity of temperature. This assembly was placed in the bottom of a long quartz tube with an inside diameter of about 1 in., which was connected to the vacuum system through a ground joint sealed with picein wax well removed from the furnace. A thermocouple tube inserted through the top of the vacuum line reached into the tantalum jacket so that the thermocouple junction was immediately adjacent to the Knudsen cell except for the protection tube wall. A resistance furnace could be raised to cover the end of the quartz tube containing the cell in such a way that the cell was in the uniform temperature zone 13 in. from the end of the furnace. An ionization gage was included in the vacuum system in the cold lines of wide diameter, immediately beyond the ground joint. The vacuum system consisted of a mercury one-stage diffusion pump, backed by a Welch duo-seal mechanical pump. The pumps were separated from the reactor chamber by a dry ice trap. The ionization gage always read less than 10-5 mm Hg after initial outgassing and before each run was started. Each newly filled Knudsen cell was evacuated at high temperature overnight before the first weighing was made. The cell was returned to the system, heated for a measured time at constant temperature, cooled, and reweighed. The heating and cooling times were quite short since the hot furnace was raised to receive the reactor at the beginning of the run and removed again at the end. The tube heated or cooled quickly. The total mass loss was attributed entirely to effusion of silver vapor from the quartz cell, since empty quartz cells maintained constant mass through similar heating cycles. The vaporized silver condensed on the cold walls of the quartz tube extending above the furnace. Earlier studies in the induction heated unit had shown that the same vapor pressure was found for silver, whether the silver was in contact with the tantalum metal cell or with porcelain or quartz liners. The Pt-Pt-10 pct Rh thermocouple was calibrated against a secondary standard of the same material and found to agree with the published tables. Always operating in air at temperatures below 100O°C,

Jan 1, 1954

By J. C. Coughlin, M. C. Flemings, T. Z. Kattamis

Experiments on Al-4.5 pct Cu alloy shou the dendrite arnz spacing increases with time during isothermal holding in the liquid-solid region. This coarsening of the dendrite structure is then shown to occur at roughly the same rate during solidification as during isothermal holding. Final dendrite arm spacing in both types of experiments depends primarily on coarsening kinetics. It is concluded that driving force for the coarsening is reduction of liquid-solid sur/ace area. Calculations based on two simple models show qualitative apreement with experinzent. 1 HERE has been considerable interest in recent years in determining effects of solidification variables on dendrite arm spacing in cast alloys. The interest has resulted primarily from the clear evidence that 1) the degree of homogeneity which can be obtained in a cast alloy with commercially practical homogeni- zation treatments depends on dendrite arm spacing, and 2) mechanical properties of the heat-treated casting depend on the homogeneity obtained.'-' In wrought alloys, microsegregation from the original ingot is carried to some extent into the final wrought product, and affects mechanical properties in similar fashion Experimental evidence available indicates that dendrite arm spacing in cast aluminum alloys is influenced only by cooling rate (or "local solidification timev*) and alloy content.Fig. 1, for example,

Jan 1, 1968

By J. S. Fulton

THOSE who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangement, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartment septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries) ; portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. PHASES Of the many papers published on various phases of the Bessemer process, nearly 170 according to one bibliography, over go per cent were concerned with the metallurgical phase and less than 10 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to one of the causes of the Bessemer process. Is it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By Arthur Knapp

NEARLY every technical man is called upon at some time in his life to deliver a paper before a technical audience or to write a technical paper for publication. It is not necessary to be an accomplished public speaker to deliver a technical paper successfully; it is only necessary to bear in mind a few obvious points. Poorly presented papers are nearly always the result of a few errors of deportment, but they are vital and at the same time so obvious that they are often overlooked. Experience is a good teacher but a little study and careful preparation will moderate the suffering of both an amateur speaker and his audience. An author's paper suffers, through poor delivery, in direct proportion to the suffering of his audience. The best test of a paper is to have it read aloud to the author. This will bring out faults not apparent when read silently by the author. Some of the things which will probably need correcting are improper phrasing, noneuphonic sequences, and long or involved sentences. Frequently authors write their papers in short crisp sentences for oral presentation, then rewrite them for publication.

Jan 1, 1942

By Robert U. Richards

THE spitzlutte, as described by Rittinger, is an instrument by which sand is sorted in a continual upward-flowing stream of water. Its usual form is that of a pointed box, placed with the point downward, the box receiving its feed of sand and water on one side and discharging its tailings on the other. The sorted product or concentration is discharged at the bottom, at the apex of the box, through which it falls against an upward current -of water, which current serves to effect the sorting and separation. To make this exposure to the quicksand condition still more effective, an inverted dam is placed across the spitzlutte, which forces the sand in its passage from the feed side to the discharge to pass down into the more active portion of the upward-flowing current of water. In the form adopted for small tests in the mining laboratory of the Massachusetts Institute of Technology (see accompanying sketch) the feed is through a central funnel instead of being at the side, and the apex of this funnel, extending down nearly to, the apex of the cone, takes the place of the inverted dam in the large spitzlutte. To keep the experiment perfectly under control a bulb or bottle is attached by a rubber connecting-tube to receive the concentrations, and between this bottle and the apex of the spitzlutte is placed -1 glass tube of conical form, with a side tube for the admission of water. By regulating the admission of water through this tube the concentration may be allowed to go down into the bulb as fast or as slowly as the richness of the ore seems to demand. This spitzlutte may be used on products that have been previously sized to take out the heavy mineral. As, an example of this a test was made upon a' sample of ore where the galena, blende, and quartz were much mixed up, but separated fairly when crushed. The sample of ore was from Newburyport, and assayed 16.50 per cent. lead.. After sizing through a series of sieves the ore yielded concentrations and tailings to the spitzlutte as follows

Jan 1, 1881

By R. H. Richards

The spitzlutte, as described by Rittinger, is an instrument by which saud is sorted in a continual upward-flowing stream of water. Its usual firm is that of a pointed box, placed with the point downward, the box receiving. its feed of sand and water on one side and discharging its tailings on the other. The sorted product or concentration is discharged at the bottom, at the apex of the box, through which it falls against an upward current of water, which current serves to effect the sorting and separation. To make this exposure to the quicksand condition still more effective, an inverted dam is placed across the spitzlutte, which forces the sand in its passage from the feed side to the discharge to pass clown into the more active portion of the upward-flowing current of water. In the form adopted for small tests in the mining laboratory of the Massachusetts Institute of Technology (see accompaaying sketch) the feed is'throogh a central funnel instead of being at the side, and the apex of this funnel, extending down nearly to the apex of the cone, talks the place of the inverted dam in the large spitzlutte. To keep the experiment perfectly under control a bulb or bottle is attached by a rubber connecting-tube to receive the concentrations, and between this bottle and the apex of the spitzlutte is placed a glass tube of conical form, with a side tube for' the admission of water. By regulating the admission of water through this tube the concentration may be allowed to go down into the bulb as fast or as slowly as the richness of the ore seem.; to demand. This spitzlutte may be used on products that have been previously sized to take out the heavy mineral. As an example of this a test was made upon a sample of ore where the galena, blende, and quartz were much mixed up, but separated fairly when crushed. The sample of ore was from Newburyport, and assayed 16.61) per cent. lead.. After sizing through a series of sieves the ore yielded conceutrations and tailings to the spitzlutte as follows :

Jan 1, 1881

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly '7' according to one bibliography, Over go per 'ent were concerned with the metallurgical phase and less than '0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly '7' according to one bibliography, Over go per 'ent were concerned with the metallurgical phase and less than '0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By D. K. Atwood

Experiments resulted in a satisfactory laboratory method for restoring permeability to clay-containing cores damaged by fresh water. Clay contents of a number of field cores were measured, and permeabilities of plugs from these same cores were then deliberately reduced with fresh water. This damage is attributed to swollen and dispersed clays occupying the pore space. After damaging, a number of experiments were performed to meaJure the amount of damage and to establish some means by which permeability could be restored. The experiments included flooding the damaged cores with water-miscible fluids such as salt water, acetone, isopropyl alcohol and ethanol. Permeability was not successfully restored in these experiments. However, part of the damage was repaired by flooding with oil; when water was removed by distillation in the presence of immiscible fluids such as air or toluene, permeability was completely restored. This evidence suggested that swollen and dispersed clays could be collapsed to their original volume by strong interfacial and capillary forces. It was further postulated that the required forces could be generated by flooding the damaged cores with a solvent partially miscible with water. The flooding experiments were repeated using n-hex-an01 as the partially miscible solvent. Permeability was restored to five of six damaged cores and substantially increased in the sixth. A large fraction of the restored permeability was retained even after water saturation was raised to its original value with 12 per cent salt water. INTRODUCTION Sharp reductions in permeability often occur when relatively fresh water contacts clay-containing formations during drilling and workover operations. These permeability losses are caused by removing inorganic ions from the environment surrounding the clay, and consequent swelling and/or dispersion of clay minerals into the available pore space.' This phenomenon is generally termed clay damage, fresh-water damage, or simply formation damage; it causes large losses in current revenue by preventing oil wells from making their allowable production. Attempts to repair the damage and restore permeability by flowing salt water solutions or brines through clay-damaged cores containing montmorillonite have been unsuccessful.' This irreversibility is thought to result from formation of brush-heap, or edge-to-face, structures when the dispersed clay is flocculated. The brush-heap structures occupy much more space than the close packed domains present before damage.' One solution of the problem is to destroy the clay-water brush-heap and thus restore permeability. Because no satisfactory method existed for restoring permeability to clay-containing formations damaged by fresh water, the work described in this paper was under taken. The laboratory experiments generally consisted of deliberately damaging fresh cores containing clay and then attempting to repair this damage by various means. Results indicate that generating strong interfacial forces within the pore space of damaged cores collapses the clay brush-heap and restores permeability. These forces are most conveniently generated by flowing partially water-miscible solvents, such as n-hexanol, through a core. THEORY OF THE DAMAGE PROCESS The most common clay mineral groups known to cause permeability damage to formations are the mont-morillonites, kaolins, chlorites and illites. These clays are constructed of particles which can adsorb water on their surfaces and edges and, in the case of montmorillonite, between layers of the basic particle itself. This adsorption increases as water salinity decreases. At low salinities the particles disperse into the aqueous phase. When the clays present in the formation are kaolin, chlorite and illite, dispersion accounts completely for permeability damage to porous media. However, unlike the other clays, montmorillonite particles can imbibe water and adsorb ions between layers of sub-particles, or platelets. These platelets have net negative charges on their faces and are held together by exchangeable (or removable) cations such as Na and Ca decrease in ion concentration (salinity) in the fluid surrounding a particle causes migration of water into the clay layers and disperses the basic particle, while diffusion removes the original exchangeable ions from between the platelets. Once these ions are removed, the facing negative platelets repel each other, causing the montmorillonite to swell until, for all practical purposes, the individual platelets are dispersed. For this reason, fresh-water* damage is much more severe in sands containing montmorillonite than it is in sands containing other clays. Many investigators have shown that even trace amounts of montmorillonite can be responsible for marked reduction in the permeability of reservoir sands in the presence of fresh water." ." Monaghan and others have shown that fresh-water damage in montmorillonite-containing cores cannot be

Jan 1, 1965

By J. A. Berger, R. J. Towner

The pjPocesses of polygonization and subgrain growth were followed in slightly stretched 99.99 pct A1 single crystals heated for cumulative times at 400°, 500°, and 600°C. Changes in sub-grain size and boundary angle were determined from measurements on X-ray micrographs. CAHN1, 2 studied polygonization in stretched and heated aluminum single crystals of 99.99 pct A1 using various techniques, including etch pits, Laue patterns, and a slight restretching of heated specimens to reveal small changes in lattice orientation by the direction of new slip lines. He found that kink bands, which had well-defined boundaries lying in a plane perpendicular to the slip direction (at least in the early stages of deformation), formed during stretching. Also, he noted that bending occurred about the <211> axis lying in the (111) slip plane perpendicular to the <110> slip direction. His studies of polygonization were largely confined to the kink bands rather than to the weakly bent matrix regions between bands. The minimum temperature required to bring about polygonization was established at about 450 "C. Guinier and Tenevin used a focusing Laue X-ray diffraction technique to study polygonization in aluminum single-crystal specimens of 99.99 pct purity. Stretching the crystals 5 pct in tension caused a widening of the focused Laue spots. After heating for 4 hr at 450°C, their method revealed no change in the specimen. Above 450°C polygonization was detected and further annealing near 600°C led to subgrain growth. They concluded that the orientation of the crystal relative to the axis of deformation had no marked effect on polygonization. Gay and Honey-combe4 using an X-ray microbeam technique found that polygonization did not occur in a stretched aluminum crystal heated at 250oC, although some decrease in the yield strength occurred. When the temperature was raised to 475oC, the asterism became broken up as a result of polygonization. Honeycombe5 noted that reflections on X-ray mi-

Jan 1, 1961

By E. R. Smith

ANALYSIS of the requirements for gun perforation equipment suitable for penetrating casing and cement showed that these points would be involved: (1) Powder charges electrically detonated under high fluid lieads and at remote distances. (2) Selective firing of sliots in sequence. (3) Sufficient velocity for the bullet to penetrate at least two strings of seamless casing and all cement beyond the strings. (4) Heat-treatment of steels to withstand great pressures and penetration. (5) Esclusiorl of fluid under extremely high hydrostatic pressure. (6) Stranded steel wire line acting as weight - suspending and current - carrying medium. (7) Firing controls operated above the surface. (8) Determining gun depth and suspended weight by means of the wire line. (9) Portability for field use.

Jan 1, 1936

By George A. Komadina

From its modest beginning in 1957 with one mill grinding section handling 3000 tpd Pima has steadily expanded. In July 1966, work was completed that allowed the concentrator to treat in excess of 18,000 tpd. Almost immediately Pima embarked on another expansion program that will increase plant capacity to 30,000 tpd during the summer of 1967. This repeated expansion has corresponded with the development of additional low-grade ore deposits and with the improved operating economics realized by handling larger masses of material. Early in the life of Pima it was known that a mineralized area was present on the flanks of the high-grade orebody which systematic drilling had shown to be a low-grade copper orebody. Many months of engineering studies revealed that this was sufficient to allow Pima to compete with other large scale, low-grade copper operations in the Southwest.

Jan 11, 1967

By Raymond Mancha

TO determine the optimum inside dimension of an airshaft, it is necessary to strike the proper balance between the cost of power for air friction and turbulence losses within the airshaft, on the one hand, and the cost of sinking the airshaft, on the other. An airshaft larger than necessary is extravagant because the increased amortization rate exceeds the reduction in power cost. Conversely, an airshaft smaller than is needed wastes more power than can be justified by the corresponding reduction in amortization rate. The airshaft power is a function of the air volume Q cu. ft. per min. and the air- pressure drop p in. water gauge across the airshaft The airshaft pressure drop is calculated by the formula: [ ] wherein R is the air-friction coefficient for the portion of the airshaft 1 ft. deep, 0 ft. in perimeter and A sq. ft. in area, when passing an air volume of Q cu. ft. per minute. The airpower w kw. dissipated within the airshaft is computed by the formula: [ ] With a combined over-all unit efficiency of the fan and drive of E per cent, the air- shaft power requirements become [ ] There are 8760 hours per year, so with energy at I cent per kilowatt-hour the annual cost per kilowatt for continuous operation is $87.60; therefore, with energy at C$ per kw-hr. the annual airshaft power cost MI dollars per year becomes: [ ] which, expressed by the component parts, becomes : [] The amortization rate a dollars per year per dollar invested includes both depreciation and interest on the investment. These in turn involve the expected useful life of the airshaft and available monetary interest rate. For the purpose of this discussion the cost of airshaft sinking is assumed to comprise a fixed move-in charge Y dollars, which covers the cost of transporting, erecting and removing the shaft-sinking equipment and is independent of the air- shaft size. Also, it is assumed that the cost of shaft lining, if any, is fixed at $X per cu. yd. of lining material and that excava-

Jan 1, 1946

By A. E. Lee

THE Blackwell Zinc Co., Inc., a subsidiary of the American Metal Co., Ltd., operates a horizontal retort zinc smelter at Blackwell, Okla. The plant has 14 furnace blocks of 800 retorts each, fired with natural gas on a 48 hr cycle. Over 13,000 tons of zinc-bearing material, chiefly sulphide flotation concentrates, are treated monthly to produce slab zinc and high lead-cadmium fume. In 1942 a program of rebuilding and modernizing the smelter was started. By 1947 furnace smelting capacity had been increased to a point where roasting and sintering facilities were inadequate, and it was necessary to purchase oxidized materials to supplement sinter production. The seven 210 ft Ropp roasters and three 42 in. x 44 ft Dwight-Lloyd machines then in use had been in service at least 20 years and were in need of major rebuilding. Thus it was entirely practical to consider all new equipment and a change of method rather than rebuilding and repairing obsolete units. A study of the problem indicated that roasting as such could be eliminated and roasting and sintering accomplished in one step by a modification of the Robson process,&apos; which had been used since the early 1930&apos;s by the National Smelting Co., Ltd., at their plants at Avonmouth, England, and Swansea Vale, South Wales. Francis P. Sinn, General Manager, Zinc Smelting Operations, The American Metal Co., Ltd., who was familiar with the practice in England, suggested the use of one large machine for the entire operation from concentrate to sinter. One step sintering appeared to best meet Blackwell&apos;s plant requirements and indicated substantial savings in labor, gas, coal, and repair costs. Choice of Machine Size The sinter machine size was set at 12x168 ft for a rated capacity of 540 tons per day. This tonnage, produced on a five day week, would meet the seven day requirements of the 14 furnace blocks. The one large machine was quoted at a lower cost than two or more 6 ft wide machines of similar total capacity. Further, the larger machine could be housed in a smaller structure and only one set of equipment for charge preparation and delivery and for disposal of sinter cake was needed. One machine on a five day week made possible a concentration of the skilled operating personnel and required less men than a plant including two or more machines and related equipment circuits. Fewer units of equipment meant less maintenance, and the two down days weekly allowed ample time to repair and, if necessary, to make up lost production. Experience had indicated better sintering quality and rates with larger masses of material, not only on wider machines, but also in deeper beds. The ratio of windbox perimeter to area for the 12x168 ft machine is 0.179, compared to 0.353 for a 6x102 ft machine and 0.617 for a 42 in. x 44 ft machine. This meant less air leakage with resulting fan power savings and less spoilage of charge along the pallet sides. Performance Initial operation of the new sinter plant was made in November 1951 and regular production attained late in December. The average product sinter output during 1952 and the first half of 1953 has been 18.2 tons per hr. The average for one month has been as high as 22.4 tons per hr. Considerable experimenting with varied operating conditions accounts in part for the below capacity — 24 tons per hr — average output, and work to further improve production rate continues. A typical sinter analyses is 66.0 pct Zn, 0.3 pct Pb, 0.1 pct Cd, 0.3 pct S, 8.0 pct Fe, 2.0 pct SiO,, 0.8 pct CaO, and 0.2 pct MgO. Use of this material has made possible increases in furnace burden and improved furnace operation over the former practice using sinter made from Ropp roasted concentrates. Better lead and cadmium elimination in sintering has permitted the furnace production of slab zinc lower in lead and cadmium. Anticipated economies of operation have largely been gained. The sinter plant is operated by seven men per 8 hr shift — one head operator, three equipment operators and three sweepers — plus one oiler on day shift only. While it has been necessary at times to operate seven days a week to produce the required sinter tonnage, the five day work week usually has been adequate. Consumption of natural gas for sinter bed ignition is 200,000 to 300,000 cu ft per day. Green Ore Sintering Practice The 30 to 31 pct sulphur content of the —200 mesh zinc concentrates is the fuel used to sinter the charge, no coal addition being required. In the feed to the machine, sufficient concentrates are added to crushed return sinter fines containing 0.3 to 0.5 pct sulphur to produce a charge averaging 5.0 to 6.5 pct sulphur. Since the return sinter used in Blackwell&apos;s practice is varied from — 1/2 to — 1/8 in., the actual sintering mixture of fine sinter and concentrates is somewhat higher in sulphur. The coarser sinter particles are too large to resinter and merely aid porosity in the sinter bed. The ratio of concentrates to return sinter in the charge ranges from about 1:4 to 1:5.5. Variations are based on the appearance of pried up bed sections, bed exit gas temperature trends, windbox suctions, and return sinter size. Sufficient sulphur must be used to obtain fritting of the charge into a soft sinter cake and to aid in the elimination of lead and cadmium. Excessive feed sulphur will result in partial slagging of the cake impairing porosity and prolonging sintering time.

Jan 1, 1954