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By J. Leja, A. Pomianowski

This paper deals with equimolar solutions of xanthate and alkyl trimethyl ammonium bromide adsorption on copper, nickel and sphalerite powders. After an exposition of the experimental methods used and the results obtained, a thorough discussion leads to the conclusion that some molecular association between xanthates and CnTAB's does take place in the bulk of the solution as well as at the air/liquid interface. A spectrophotometric study of xanthate solutions alone and their mixtures with equimolar amounts of alkyl trimethyl ammonium bromide (CnTAB) has established the additivity of ultraviolet spectra (190 to 400 mµ) for potassium ethyl xanthate (KEtX) and C12TAB. No obvious effect of C12TAB addition on the decomposition rate of KEtX was observed, the half life of which was established as 29±3 days at 22°C and pH ~ 6. In mixed solutions of longer xanthate homologues (e.g. hexyl and nonyl) and equimolar CnTAB, colloidal precipitates are gradually formed which contain primarily the corresponding xanthate molecules. The kinetics of collector abstraction by copper, nickel and sphalerite powders were studied in 10-5 to 10"3 M solutions of KEtX alone and in equimolar mixtures of KEtX and CI2TAB. Presence of C12TAB caused a two to three fold increase in the amounts of xanthate (equivalent to many monolayers) abstracted by copper and nickel powders (and in their rates of abstraction) but had no effect on the abstraction of xanthate by unactivated sphalerite (equivalent to less than a monolayer). The adsorption of C12TAB itself from the mixed solutions was very low, at most one monolayer only, and was not influenced by the nature of the solid powder used. A change in the rates of abstraction, observed with copper powder, was interpreted as a completion of a multilayer coating (completely enveloping the grains of powder) following which the rate of reaction between solution and substrate becomes controlled by diffusion through this coating. Work of Buckenham and Schulmanl on molecular associations between different collectors has shown unusual synergistic effects in flotation of individual minerals using mixtures of xanthates and alkyl trimethyl ammonium bromides. The objectives of the present work were: 1) to determine whether these molecular associations between the two types of collectors (indicated by strong surface tension lowering in Buckenham and Schulman's work) take place at the air/liquid interface only or in the bulk of solution as well 2) to establish whether different solids adsorb any species from the mixture of these amphipatic molecules preferentially or as molecular complexes 3) to establish whether there are any differences in the kinetics of adsorption. Metallic copper and sphalerite powder were chosen as adsorbents since they represent two extremes since copper readily adsorbs multilayers of xanthate (and is easily floated with ethyl xanthate) while unactivated sphalerite does not appreciably adsorb xanthate but is known to be readily floated by the amine type collectors. Metallic nickel was included because the infrared spectroscopic work2 on xanthate

Jan 1, 1964

By F. X. Spiegel, D. Bardos, Paul A. Beck

Ti6NileSi7)G is known to be cubic, with 116 atoms in the unit cell. In the present work four new G sili-cides were found with other transition elements and five G germanides. The titanium-group elements are very efficient in forming G phases. The vanadium -group elements are somewhat less efficient, and the chromium-group elements do not form any. Cobalt can replace nickel in most cases, but it is somewhat less efficient. Iron was not found to form any G phases. Germanium is somewhat less efficient than silicon. The (TiNiSi)E phase has been previously identified by Westbrook. However, its crystal structure has not been determined. In the present work the E phase was found to have an orthorhombic unit cell with lattice parameters a. = 7.02, bo = 5.18, co = 11.11A. A large number of other E phases were found at the same stoicheometric ratio in ternary systems of silicon and germanium with transition elements. Lattice parameters similar to those for TiNiSi were measured. The number of atoms per unit cell is estimated at 30 to 36. The vanadium-group elements are somewhat more efficient in forming the E phase than the titanium-group elements. Chromium-group elements were not found to form any E phases. Cobalt is somewhat less efficient than nickel, and iron is less efficient than cobalt. Germanium is not as efficient as silicon. ThE ternary silicide designated as G-phase was first identified by Beattie and versnyder1 and by Beattie and Hagel2 at the approximate composition TiNi2Si. Westbrook et al.' gave the composition as Ti2Ni7Sis. This phase was found to be fcc with a. = 11.201A and 116 atoms per unit cell. Beattie4 and more recently independently Hladishevskii, Kripyakevich, Kuzma, and Teslyuk5 were able to show that this structure is isotypic with MgeSi7CuLe and Th6Mn23. The latter structures had been determined by Florio, Rundle, and snow,' Nagorsen and Witte,7 and Bergman and Waugh.8 According to the crystal structure, Ti8Ni6Si7 may be considered as the ideal composition. The Russian investigators5 identified six additional ternary phases isotypic with Ti6Ni6Si7, in which titanium is replaced by Mn, V, Nb, Ta, Zr, and Hf, and one, namely MneNil6Ge7, in which germanium replaces silicon. They also found that Cr6Ni6Si7, which does not occur as a ternary phase, can be stabilized by replacing 1 at. pct of the Cr by V, Mn, or Ta. Another ternary silicide was found by Westbrook et al.3 at the composition TiNiSi, and it was designated by them as the E phase. The crystal structure of this phase has not been deter-

Jan 1, 1963

By Richard M. Foose

MOST of the roofing granules produced in Pennsylvania are made by two companies at three plants. The Advance Industrial Supply Co. has three quarries and a mill at Gladhill Station, in southern Adams County. The Funkhouser Company is actively engaged in mining, quarrying and milling at Charmian, about one mile west of Gladhill Station, and at Delta, in southern York County. These three plants produced approximately 100,000 short tons of granules in 1943. The production of roofing granules in 1937 for the whole country was only about 500,000 tons, generally indicating the large growth of the industry since that time. The fundamentals of producing roofing granules were discussed comprehensively by G. W. Josephson in a paper before the Industrial Minerals Division in October 1943 (Mining Technology, March 1944). The purpose of this paper is to describe the actual methods of mining the rock and milling it to make roofing granules, as practiced by the three Pennsylvania plants. MINING AND MILLING Funkhouser Company (Delta) The Funkhouser Company, near Delta, in southern York County, Pennsylvania, operates three joined quarries and a mine in the Peach Bottom slate. The joined quarries extend 1200 ft. in a northeast southwest direction along the strike of the slate cleavage and are about 200 ft. wide. The working face is about 45 ft. high. The quarrying operation is rather simple: Ingersoll-Rand Jackhamers, 1-in. and 1 1/4-in., with hollow drill steel, are used to undercut the quarry face with10-ft. holes. The face is "blown" and allowed to slump on the quarry floor. Loaded by a Marion electric shovel into trucks, the shattered rock is taken to the primary crusher 2500 ft. away. In addition to the normal quarrying operations, a drift into the northeast wall of the middle quarry was begun about 1935 and has advanced about 2000 ft. since then. Rooms have been driven at angles to the drift along choice beds of slate. The drifts and rooms have a roof more than 35 ft. high and the main drift and rooms are all more than 40 ft. wide. There is no cribbing at any place in the mine. Several of the rooms were driven upward on a 5º slope and in some of them there was stoping. Ingersoll-Rand Jackhamers are used, and only wet drilling is practiced. When visited in January 1940, an electric shovel was operating at the head of the drift, scooping up the slate blasted out of the working face. This, too, is trucked to the primary crusher. Some of the better quality slate is saved for making slate shingles. The primary crusher, which is a No. 30 McCulley gyratory, receives the slate from the trucks and crushes it to about 2-in. size (Fig. I). This product travels by a 30-in. belt conveyor to Niagara vibrating screens with 2-in. holes. The minus 2-in. product moves to a storage silo by bucket

Jan 1, 1945

By Henry H. Angst

Tim history and efficiency of 40-ton capacity dump trucks for surface waste removal at the New Cornelia opencut copper mine, at Ajo, Ariz., are summed up in this paper. Tabulations of truck performance, together with detailed cost figures, prove the value of truck transportation for certain special operations at a large mine. Emphasis is given to the fact that truck transportation not only reduces the haulage costs but also reduces the breaking ground and shovel-loading costs per ton. The New Cornelia opencut copper mine is in the desert. The climate is ideal for seven months of the year, but the five summer months are uncomfortably hot. The elevation is 1820 ft. above sea level and the annual rainfall is approximately 6 inches. The ore body is a monzonite-porphyry deposit. The waste-rock capping consists of hard rhyolite, conglomerate and porphyry. All the material is hard and cannot be excavated without blasting. The rhyolite and conglomerate waste is very blocky. The weight of the rock in place is 2.16 tons per cubic yard. The average mine production per day is 22,000 tons of ore and 18,000 tons of waste rock, the latter consisting of surface rock and material within the ore body too low in grade to send to the concentrator. The rock is loaded by electric shovels with 4 1/2-cu. yd. dippers. The primary transportation of ore to the concentrator and waste to the dumps is by 30-yd. dump cars and oil-burning steam locomotives; therefore truck haulage of waste is a minor factor of the New Cornelia operation. However, as New Cornelia was one of the first mines to use large-capacity dump trucks for haulage, the results obtained are of interest. EQUIPMENT On the south side of the New Cornelia is a hill rising about 500 ft. above the normal surface elevation, roughly 1000 ft. in diameter at its base, called locally Arkansas Mountain peak. Exploratory drilling in this area developed additional ore that could be made accessible for open pit operation only by moving the mountain face a maximum distance of 400 ft. to the south. The slope of the mountain adjacent to the pit averaged 35°, and the small area involved precluded the use of train haulage for the removal of the 4,000,000 tons of waste estimated above the normal pit elevation. A study of dump-truck haulage at Boulder Dam and San Gabriel Dam led to the decision to use large-capacity end-dump trucks rather than smaller trucks, for the following reasons: I. The truck would have to withstand the impact of hard, heavy chunks, some of them weighing as much as 10 tons, which would be dumped from the 4 ½ -cu, yd. dipper. 2. The coarse, rocky, abrasive material would soon damage a light truck body. 3. The body of a small truck could not be efficiently loaded with coarse rock.

Jan 1, 1941

By Nelson B. Russell, Donald C. Bond

The effects of various antifreeze agents on the formation of hydrogen sulphide hydrate have been studied. On a molar basis the relative lowering of Tm (the maximum temperature at which solid hydrogen sulphide hydrate can exist in equilibrium with the given solution) for the various agents is: sodium chloride 1.00, calcium chloride 1.71, methyl alcohol 0.57, ethyl alcohol 0.68, ethylene glycol 0.73, diethylene glycol 0.73, sucrose 0.87, dextrose 0.71. On a weight basis the relative lowering of TM is: sodium chloride 1.00, calcium chloride 0.91, methyl alcohol 1.08, ethyl alcohol 0.89, ethylene glycol 0.69, diethylene glycol 0.41, dextrose 0.23, and sucrose 0.15. Introduction The solid hydrate of hydrogen sulphide, H2S.6H20,1 is in equilibrium with water and liquid hydrogen sulphide at 85°F at a partial pressure of hydrogen sulphide approximately equal to the vapor pressure Of hydrogen sulphide at that temperature. At temperatures below 85°F, in the presence Of excess hydrogen sulphide (greater than the amount required to react with the water present) the hydrate is in equilibrium with liquid hydrogen sulphide at approximately the vapor pressure Of hydrogen sulphide. In the presence of excess water, the solid hydrate is in equilibrium with liquid water, containing dissolved hydrogen sulphide, at a pressure lower than the vapor pressure of liquid hydrogen sulphide at the same temperat~re.2 The lower the temperature, the greater the difference between the decomposition pressure of the hydrate and the vapor pressure of liquid hydrogen sulphide at that temperature. Conditions conducive to the formation of solid hydrogen sulphide hydrate may exist in wells producing a gas containing a high percentage of hydrogen sulphide under high pressure, or in the lead lines from such wells. This paper gives the results of tests made with various antifreeze agents which might be useful in decomposing the hydrate or in preventing the formation of the hydrate of hydrogen sulphide Apparatus Fig , shows a diagram of the apparatus used. The sample under observation was contained in a glass tube 34 cm long, having a 6 mm id and a wall thickness of 2.5 mm. The lower end of this tube was closed- with a plug of butyl rubber. The upper end of the tube was connected to a diaphragm gauge, with a stainless steel diaphragm, a manometer, a vacuum pump, and a cylinder of hydrogen sulphide, The tube was held nearly horizontal, with the liquid resting along the lower side of the tube. It was found that when the tube was held in a vertical position, it broke with ex. plosive violence as soon as it became filled with solid hydrate. Presumably this was caused by the expansion which occurred on solidification of the hydrate. The difficulty disappeared when the tube was held in an inclined position during the tests.

Jan 1, 1949

By C. E. McCarthy, A. George Stern, Stanley J. Green

THE national interest prompts consideration of any new source of mineral wealth even though the immediate need may be of minor importance. A critical shortage of potash in the United States during the World War of I9I4-I8 stimulated broad development, which established an American potash industry on a basis so sound that this commodity is not even listed as urgent in the present war program. However, this should not minimize its importance, and the need remains, not only for adequate supplies of the usual potash salts (the chloride and the sulphate) but of all potash chemicals. Potassium carbonate (known commercially as pearl ash) has been a high-cost commodity; in consequence, the quantity used by industry has been relatively small. By a combination of fortuitous geographical circumstances, there is opportunity to produce a low-cost potassium carbonate with the possibility that this might become an important source of chemical potash. The following paper considers a recently developed process1 taking advantage of these conditions. WYOMINGITE DEPOSIT For many years it has been known that a deposit of potash-bearing igneous rock known as wyomingite occurs in the southwestern part of Wyoming at Zirkel Mesa, which is 44 miles northeast of the town of Green River (Fig. I). The western escarpment of this deposit is about 3 miles east of the Superior Branch of the Union Pacific Railroad. This mesa alone covers approximately 3300 acres, and the average thickness of the wyomingite flow is 75 ft. It has been estimated2 that about one billion tons of wyomingite occur in this one deposit, all of which can be mined by open quarrying without overburden. In addition, there are several smaller deposits within 10 miles, so that the aggregate wyomingite in the area approaches two billion tons. This is one of the world's largest sources of leucite, and the only known deposit of its kind in the United States. The wyomingite (which is in the form of a lava flow and numerous small craters), with the mineral leucite as its most important component, has a mineral composition3 of: leucite, 50 per cent; phlogopite, 15; diopside, I2; kataphorite, 15; glass and apatite, 8. The phlogopite is present in visible phenocrysts 1/8 to 1/2 in. in diameter, but the leucite usually is almost microcrystalline and not capable of liberation by grinding. Chemically, the wyomingite has a potash content averaging slightly higher than eleven per cent K20. The potash is mainly in the leucite, but part of it is in the phlogopite and a small amount is in the feldspars that are occasionally seen as undigested occlusions of the granite country rock, through which the leucite-bearing lava intruded, and as sanidine feldspar both in the crystalline and glassy phases of the rock. A typical analysis of the wyomingite from Zirkel Mesa is as follows:

Jan 1, 1944

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

IT is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investigators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from 1100° to I700°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxidation of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,5 the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery6 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid,i.e., the sulphur was in combination with the silica. Orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By James M. Stapleton

IT has long been recognized by blast- furnace men that correct top distribution of materials is very important in efficient and economical furnace operation. Thousands of experiments on top design, filling, sizing, and other operations have been carried out to improving furnace performance by securing uniform distribution. Many of these experiments have worked out satisfactorily and have been passed along to the industry. Many of them have been discarded and forgotten. It has been the custom to judge the results of such experimentation by the results shown in improved or lowered furnace efficiency. While the effect on furnace practice will have to continue to be the final criterion of experimental changes, it has always been a desire of blast-furnace men to ascertain the reason for failure or success. Efficiency in the blast furnace approaching the maximum can be measured in several ways: (I) by actual operating results as revealed in the coke rate and tonnage figures, and (2), in the degree to which the top gas approaches the limiting ratio of CO/C02 for the reduction of iron oxide by CO gas. This ratio is shown in the equilibrium curve in Fig. I for the system Fe-O-C and CO2-CO-C. The closer the top gases approach this limiting ratio (set at 1.08 by Martin1 because of the effect of limestone calcination) the more efficiently we may expect a furnace to operate. The fact that low CO/C02 ratios parallel eficient operating performance caused us to investigate the cause of good or poor distribution and the effect of filling and other changes on furnace operation. Heretofore it has been possible to take a sample of furnace gas (usually from the dust catcher) and from it determine how closely the reducing gases were to the ideal or limiting value as set by the equilibrium diagram. However, to find just where in the top area the distribution was distorted and the top-gas CO/CO2 ratios were distant from equilibrium values has been a difficult and expensive investigational procedure. In an effort to overcome this difficulty, apparatus was designed to take gas samples and temperatures across the top radius of the furnace. It was hoped that with the aid of this apparatus traverse sampling of the ascending gases could be simplified, and the cost of sampling substantially lowered. Routine experimenting could then be maintained and results checked with furnace operation. It must be emphasized that a traverse sampling is necessary for a true picture, as single samples at any one point are unreliable. This statement can be verified by an examination of Tables 3 to 6, showing results obtained at our furnaces in a large number of tests. APPARATUS The design of the equipment for taking the samples was governed by the need for providing a simple, routine test that could be performed fairly quickly without adversely affecting normal furnace operation.

Jan 1, 1943

By C. W. Spencer, F. G. Hochgraf, R. F. Cheney

Columnar grained specimens of nickel, containing 0.25 pct Si and 0.22 pct Mn, have been exposed to liquid bismuth in the temperature range 670° to 1050°C. Under isothermal conditions the liquid penetration rate is constant. The activation energy for the process is 22,000 cal per g-atom. Small amounts of plastic deformation, introduced into specimens prior to exposure, increase the penetration rate. The slou. step in liquid film penetration is associated with a reaction which occurs at or near the leading edge of the film. Either transfer of nickel across the liquid-solid inteqace or diffusion in the grain boundary ahead of the liquid film is suggested. Aliquid metal, if brought into contact with the surface of an unstrained solid metal, will usually penetrate to some extent into the grain boundaries of the solid. Under isothermal conditions the extent of penetration after any particular time of exposure is related to the relative magnitudes of the interfacial tensions concerned.1,2 If the liquid-solid interfacial tension is less than one-half the grain boundary tension the liquid may penetrate at a relatively rapid rate for an indefinite distance into the grain boundary surfaces. If the liquid-solid interfacial tension is greater than one-half the grain boundary energy, liquid penetration occurs at a continually decreasing rate so that after the liquid has penetrated to a relatively short distance below the surface the process essentially ceases.3 Many observations of a qualitative nature concerning inter crystalline attack by liquid metals have been reported, for example, liquid bismuth upon copper,' liquid mercury upon brass,4 and liquid mercury upon nickel.' Scheil and Schessl determined the rate of penetration of liquid bismuth into the grain boundaries of hot rolled copper rod? At constant temperature, penetration rate was found to be independent of the depth penetrated, the rate in- creasing with increasing temperature corresponding to an activation energy of 20,000 cal per g-atom for the process. It was suggested that at lower temperatures the liquid travelled mainly along lines of three grain intersections while at temperatures greater than 1000°C essentially all grain boundary surfaces were covered. Recently, in a study of copper bicrystals having a common [loo] axis it was found that at 649°C bismuth penetrated 22, 25, and 63 deg boundaries while it did not penetrate 2, 12, 15, and 72 deg boundaries.' Elbaum reported that liquid gallium penetrates aluminum grain boundaries to a depth of 0.6 cm after 11 hr at 27°c.8 Assuming that the rate controlling step in the process was diffusion down the liquid film to the specimen surface, a diffusion coefficient of 10-5 cm2 per sec was calculated. This paper reports a study of the penetration of bismuth-nickel liquids into the grain boundaries of a nickel alloy, containing 0.25 pct Si and 0.22 pct Mn as principal alloying elements. The phase diagram

Jan 1, 1962

By J. R. Jargon, H. K. van Poollen

Non-Newtonian fluids may be injected into a reservoir during secondary recovery operations. The non-Newtonian fluid used in this work is a power-law type of fluid that is, the viscosity of the fluid decreases as the flow rate or rate of shear increases. This paper presents equations for steady-state linear and radial flow of such fluids, transient behavior results from a finite difference model of a radial system, and transient behavior results from a field test. The equations that describe the flow of a non-Newtonian fluid are non-linear and are solved numerically. Finite difference solutions are presented as curves of dimensionless pressure drop at the wellbore us dimensionless time for a constant injection rate. Solutions were obtained for 5-percent, 10-percent and 100-percent PV of a non-Newtonian fluid for injection rates of 1, 10, 100 and 1000 cc/sec and for a 5 percent PV of non-Newtonian fluid located at T = Tw' 3, 10, 20, 50 and 100 ft for a flow rate of 1 cc/sec. The buildup curves do not exhibit a stmight-line portion as is the case for Newtonian flow through porous media. Correlations also are shown for the productivity index vs rate for the computer model study and the field tests. INTRODUCTION During various secondary recovery operations non-Newtonian fluids are injected. Such fluids, in general, include thickened water and gelled fluids. The term "non-Newtonian" implies that the viscosity is not only dependent upon temperature and pressure, but also on the rate of shear that is applied to the fluid. For example, water, which is a Newtonian fluid, will have essentially the same viscosity no matter what rate of shear is applied. A pseudo-plastic fluid exhibits a decreasing viscosity when higher rates of shear are applied; a dilated fluid has an increasing viscosity with increasing rates of shear. The objective of studies performed and described in this report is to obtain relationships and mathematical and empirical descriptions of the flow of non-Newtonian fluids through porous media. Simple mathematical relationships, computer studies that include the unsteady-state behavior of such fluids, and field tests are used. PREVIOUS LABORATORY STUDIES Laboratory studies have been performed by several investigators. The fluids used in one investigationl were surfactant-stabilized dispersions of water in hydrocarbons. Its Fig. 6 is reproduced as our Fig. 1. This effective-viscosity vs frontal-velocity diagram shows that this fluid is of the power-law type over a fairly large range of frontal velocities. Gogartyl developed an equation for the effective viscosity as a function of shear rate that reduces to Eq. 2 for frontal velocities greater than about 2 ft/D. The fluid characteristics used in the present study are similar to those reported by Gogarty. Christopher and Middleman2 performed experiments with power-law fluids flowing through pipes packed with glass beads. They used a modified Blake-Koteny

Jan 1, 1970

By C. E. McCarthy, A. George Stern, Stanley J. Green

The national interest prompts consideration of any new source of mineral wealth even though the immediate need may be of minor importance. A critical shortage of potash in the United States during the World War of 1914-18 stimulated broad development, which established an American potash industry on a basis so sound that this commodity is not even listed as urgent in the present war program. However, this should not minimize its importance, and the need remains, not only for adequate supplies of the usual potash salts (the chloride and the sulphate) but of all potash chemicals. Potassium carbonate (known commercially as pearl ash) has been a high-cost commodity; in consequence, the quantity used by industry has been relatively small. By a combination of fortuitous geographical circumstances, there is opportunity to produce a low-cost potassium carbonate with the possibility that this might become an important source of chemical potash. The following paper considers a recently developed process1 taking advantage of these conditions. Wyomingite Deposit For many years it has been known that a deposit of potash-bearing igneous rock known as wyomingite occurs in the south- western part of Wyoming at Zirkel Mesa, which is 44 miles northeast of the town of Green River (Fig. I). The western escarpment of this deposit is about 3 miles east of the Superior Branch of the Union Pacific Railroad. This mesa alone covers approximately 3300 acres, and the average thickness of the wyomingite flow is 75 ft. It has been estimated2 that about one billion tons of wyomingite occur in this one deposit, all of which can be mined by open quarrying without overburden. In addition, there are several smaller deposits within 10 miles, so that the aggregate wyomingite in the area approaches two billion tons. This is one of the world's largest sources of leucite, and the only known deposit of its kind in the United States. The wyomingite (which is in the form of a lava flow and numerous small craters), with the mineral leucite as its most important component, has a mineral composition3 of: leucite, 50 per cent; phlogopite, 15; diopside, 12; kataphorite, 15; glass and apatite, 8. The phlogopite is present in visible phenocrysts 1/8 to 1/2 in. in diameter, but the leucite usually is almost microcrystalline and not capable of liberation by grinding. Chemically, the Wyomingite has a potash Content averaging slightly higher than eleven per cent K2O. The potash is mainly in the leucite, but part of it is in the phlogopite and a small amount is in the feldspars that are occasionally seen as undigested occlusions of the granite country rock, through which the leucite-bearing lava intruded, and as sanidine feldspar both in the crystalline and glassy phases of the rock. A typical analysis of the wyomingite from Zirkel Mesa is as follows:

Jan 1, 1948

By A. George Stern, Stanley J. Green, C. E. McCarthy

The national interest prompts consideration of any new source of mineral wealth even though the immediate need may be of minor importance. A critical shortage of potash in the United States during the World War of 1914-18 stimulated broad development, which established an American potash industry on a basis so sound that this commodity is not even listed as urgent in the present war program. However, this should not minimize its importance, and the need remains, not only for adequate supplies of the usual potash salts (the chloride and the sulphate) but of all potash chemicals. Potassium carbonate (known commercially as pearl ash) has been a high-cost commodity; in consequence, the quantity used by industry has been relatively small. By a combination of fortuitous geographical circumstances, there is opportunity to produce a low-cost potassium carbonate with the possibility that this might become an important source of chemical potash. The following paper considers a recently developed process1 taking advantage of these conditions. Wyomingite Deposit For many years it has been known that a deposit of potash-bearing igneous rock known as wyomingite occurs in the south- western part of Wyoming at Zirkel Mesa, which is 44 miles northeast of the town of Green River (Fig. I). The western escarpment of this deposit is about 3 miles east of the Superior Branch of the Union Pacific Railroad. This mesa alone covers approximately 3300 acres, and the average thickness of the wyomingite flow is 75 ft. It has been estimated2 that about one billion tons of wyomingite occur in this one deposit, all of which can be mined by open quarrying without overburden. In addition, there are several smaller deposits within 10 miles, so that the aggregate wyomingite in the area approaches two billion tons. This is one of the world's largest sources of leucite, and the only known deposit of its kind in the United States. The wyomingite (which is in the form of a lava flow and numerous small craters), with the mineral leucite as its most important component, has a mineral composition3 of: leucite, 50 per cent; phlogopite, 15; diopside, 12; kataphorite, 15; glass and apatite, 8. The phlogopite is present in visible phenocrysts 1/8 to 1/2 in. in diameter, but the leucite usually is almost microcrystalline and not capable of liberation by grinding. Chemically, the Wyomingite has a potash Content averaging slightly higher than eleven per cent K2O. The potash is mainly in the leucite, but part of it is in the phlogopite and a small amount is in the feldspars that are occasionally seen as undigested occlusions of the granite country rock, through which the leucite-bearing lava intruded, and as sanidine feldspar both in the crystalline and glassy phases of the rock. A typical analysis of the wyomingite from Zirkel Mesa is as follows:

Jan 1, 1948

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By F. N. Rhines, W. S. Pellini

In many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummerl have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium of experimentation. New values obtained in this way are believcd to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by X. S. Dean2 and by E. E. Schumacher and F. C. Nix. Their points are represented in Fig. I. In their work the solidus was not located at antimony collcentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228OC.; J. E. Stead,7 24g°C.; Campbell,8 228°C.; W. Gontermann,9 245' to 252°C.; R. Loebe,lo 245°C.; E. Heyn and 0. Bauer,ll 245°C.; H. Endo,12 250°C.; R. S. Dean,= 247' to 258°C.; E. Abel, O. Redlich, and J. Adier,13 245°C.; W. Broniewski and L. Sliwowski,14 250' to 252°C.; H. Seltz and B. De Witt,4 25o°C. A temperature of 247°C. appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 247°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1943

By J. D. Sullivan, Chester R. Austin, J. L. Nunes

It is characteristic of most shales and surface clays that a bloated or vesicular structure is produced by burning to a sufficiently high temperature, usually about 150° to 200°F. above the normal maturing temperature used when making common brick of the same material. Early investi-: gators recognized this phenomenon and attributed it to the release or expansion of gases in the vitrified piece. A number of theories have been advanced on the source of the gas and the manner in which it is evolved, but none has been proved conclusively. T. E. Jackson's1 early theory that bloating was due to oxygen evolved by ferric oxide in forming ferrous oxide or ferrous silicate was never substantiated by - experimental work. Orton2 thought this explanation unlikely, as all clays should bloat at the same temperature, if this were true. He found that clays bloated in the range from IIoo° to 17oo°C. Also, many clays containing iron did not bloat at all, but fused. Orton also stated that oxida- tion of different types of carbon was a source of gas during burning of clay and should be expelled before vitrification was reached. Seger3 said that he had dissolved ferric oxide in glass with no apparent evolution of gas. Matson4 came to the conclusion that ferruginous clays burned ' to vitrification in an oxidizing atmosphere did not have the iron in a ferrous form. According to Wilson,= the gases responsible for bloating might be entrapped air, water, sulphur dioxide, carbon monoxide, oxygen, and hydrocarbons. He spoke of two causes of bloating: (I) incomplete oxidation below the vitrification temperature, and (2) decomposition of compounds and evolution of gases above the vitrification temperature. Decomposition of calcium sulphate was given as the principal example of the latter. Bleininger and Montgomery0 stated that if any time after vitrification began the evolution of gaseous matter was rapid enough so that pressure was produced within the clay, bloating was certain to take place, and a vesicular structure would be formed. They recognized that initial structure, rate of heating, kiln atmosphere, and many other variables affected bloating. Work done by the Emergency Fleet Corporation7 indicated that clays suitable for bloating should be high in compounds of metallic oxides, carbon, sulphur, sodium, potassium, or other equivalent compounds, which either act as a flux or give off gas. Orton2 studied the chemical status of the carbon, iron, and sulphur in clays during various stages of burning, using a Huron shale that bloated under oxidizing or reducing conditions. He found that only a small amount of sulphur remained in the clay and that it could be detected only by dissolving the clay in hydrofluoric acid; i.e., the sulphur was in combination with the silica. orton said that this sulphur was probably in the form of iron sulphide dissolved in the glass phase. The iron sulphide was not broken down by heating, but was dissolved in the basic slag or glass,

Jan 1, 1942

By W. S. Pellini, F. N. Rhines

In many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummerl have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium of experimentation. New values obtained in this way are believcd to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by X. S. Dean2 and by E. E. Schumacher and F. C. Nix. Their points are represented in Fig. I. In their work the solidus was not located at antimony collcentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228OC.; J. E. Stead,7 24g°C.; Campbell,8 228°C.; W. Gontermann,9 245' to 252°C.; R. Loebe,lo 245°C.; E. Heyn and 0. Bauer,ll 245°C.; H. Endo,12 250°C.; R. S. Dean,= 247' to 258°C.; E. Abel, O. Redlich, and J. Adier,13 245°C.; W. Broniewski and L. Sliwowski,14 250' to 252°C.; H. Seltz and B. De Witt,4 25o°C. A temperature of 247°C. appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 247°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1943

By Fred C. Bond

Many grindability tests have been made in the Allis-Chalmers laboratory since the tabulated results were last published.' The lists of standard ball-mill and standard rod-mill grindability tests are brought up to date in this paper, and considerable new material is added. This includes a tabulation of open-circuit grinding tests, with impact and compression-crushing tests. The standard ball-mill grindability tests (Table I) were made in a standard laboratory ball mill, 12 by 12 in. inside, running at 70 rpm, with a charge of 285 iron balls ranging from 1½ to 3/4 in. in diameter and weighing 20,125 grams. Seven hundred cubic centimeters of minus 6-mesh stage-crushed dry feed was used, and the circulating load was maintained constant at 250 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 28 to 200, and the grindability is the number of net grams of screen undersize produced per revolution. The table includes 479 tests. It has been calculated that the ball mill does 52.3 joules of useful work on the ore per revolution2 with 93 joules input to the mill. The standard rod-mill grindability tests (Table 2) were made in a laboratory tilting rod mill, 12 in. in diameter by 24 in. long inside, with a wave-type lining, running at 46 rpm. The grinding charge consisted of six I1/4-in. diameter and two 13/4-in. diameter steel rods, all 21 in. long and weighing 33,380 grams. The mill was rotated level for eight revolutions, then tilted up 5' for one revolution, down 5° for one revolution, and returned to level for eight revolutions. It was discharged by tilting downward at 45° for 30 revolutions. Feed consisted of 1250 cc of minus in. stone and the circulating load was maintained constant at 100 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 3 to 65, and the rod-mill grindability is the number of net grams of screen undersize produced per revolution. The table includes 105 tests. The impact and compression-crushing tests (Table 3) are given in a table that is an extension of a previous publication8 in which the method of testing was described in detail. Two equal hammers weighing about 30 lb each were arranged to strike simultaneous blows on opposite sides of the test specimen. Broken pieces of rock passing a 3-in. square and retained on a 2-in. square were set up with the smallest dimension between the hammers, and this distance was measured. The height of the hammers was increased slightly before each blow until the specimen broke, and the foot-pounds per inch of thickness was calculated. Ten pieces

Jan 1, 1949

By W. J. Babyak

The habit planes for hydride precipitation in large grains of alpha zirconium and Zircaloy-4 were determined in specimens containing 161 and 136 ppm hydrogen, respectively. In zirconium, the hydride platelets precipitated on various pyramidal planes inclined to the basal plane at angles ranging from 10 to 50 deg and 75 to 90 deg. Hydrides were most frequent at inclinations of about 20 deg and 90 deg. In Zircaloy-4, hydride plates were inclined to the basal plane at angles vanging from 5 to 25 deg with the predominant inclinatioiz equal to 12 deg; no platelets were found near the prism plane position. In both zircoinium and Zir-caloy-4, hydrides were principally, but not exclusively, parallel to (1011) type planes. When the Zircaloy-4 gmins were subjected to tension stresses of 12,100 psi and 19,400 psi during hydride precipitation, the hydride habit was unchanged except that precipitation favored those habit planes which were inore nearly perpendicular to the stress direction. The stress-orientatioiz effect increased with the magnitude of the stress. THE hydride habit plane in a zirconium has been determined by several investigators. Langeron and Lehr1 in 1956 found platelets parallel to (1010) slip planes. In 1962, Westlake and Fisher2 confirmed these findings and showed that hydride precipitation on twin planes, as reported by Kunz and Bibb,3 was probably due to incomplete removal of worked metal from specimen surfaces. Secondary habit planes, ( 1011) and (1015), were also found by Westlake and Fisher under particular charging conditions where a hydride layer may have existed at the hydrogenation temperature. Most recently, walters4 and westlake5 again observed the (1010) habit exclusively in zirconium. Louthan and hgermans have reported that hydrides precipitate on various ( 101l ) and (112l) planes positioned 31.5 to 90 deg to the basal plane in Zircaloy-2. The present investigation was concerned with the hydride habit in Zircaloy-4 in relation to that in zirconium and the possible change in habit when precipitation occurs under stress. The latter consideration was prompted by the stress-orientation phenomenon originally reported by Marshall and Louthan.7, 8 I) EXPERIMENTAL Materials and Specimens. Chemical analyses of all materials are given in Table I. The zirconium specimen was a 1 by 4 in. section cut from wrought crystal bar that was hot-rolled at 790°C to 0.300 in. and cold-rolled to a final thickness of 0.095 in. All surfaces were mechanically polished and then chemically polished with a solution of H2O, HNO3, and HF (10:10:l by volume) prior to annealing. Grains as long as 0.25 in. were grown by thermally cycling the specimen three times (in 10-5 mm Hg vacuum) between 825" and 1000°C at approximately 125°C per hr. The specimen was isothermally annealed at 825°C for 24, 40, and 120 hr after each cy-

Jan 1, 1968

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (— 325-mesh) sand assaying 95.5 per cent SiO2, and a very he (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fractioh was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1947

By Herbert H. Kellogg

Deposits of high-silica kaolinite clays occur at many places in central Pennsylvania. These white clays were formed apparently by weathering of argillaceous quartzite and limestone. Their geology, distribution and use have been reported by Leighton.1 The larger deposits have been mined from time to time, and the clay, after washing to remove coarse sand, has found use as rubber filler, foundry clay, and in white cements. In general, the clay from these deposits contains too much grit (quartz) to be useful as paper filler, and the silica content is too high to make it useful as china clay for ceramic ware. Gravity methods for the separation of quartz from these clays have failed because of the extremely fine size of the quartz grains, but by the methods of froth flotation described in this paper these sandy kaolins can be made to yield a purified kaolinite that has a chemical composition close to that of good-grade Georgia kaolins, and is free enough from grit to be used as a paper filler. As by-products of the separation, a fine (— 325-mesh) sand assaying 95.5 per cent SiO2, and a very he (—3-micron) clay are produced. The possible ceramic uses of these products are being investigated at The Pennsylvania State College. Experimental Procedure The Sample.—The clay sample used in these tests was obtained from a small mine near Tyrone, Pa. It had already been washed to remove coarse sand, and represented the finished product of this small mine and washery. Microscopic examination showed that the clay was composed almost entirely of the minerals quartz and kaolinite, and that the quartz was present mostly in particles larger than one micron, while the kaolinite particles generally were less than 20 microns in size. The kaolinite and quartz particles were physically separable by blunging the clay in water with a suitable dispersant. Preparation of Flotation Feed.—By the addition of NaOH in an amount equal to 3 lb. per ton of solids, the clay was completely dispersed in water. Flotation feed was prepared by allowing a dispersed suspension (10 per cent solids) of the clay to stand for the period of time required for a 2.5-micron particle of quartz to settle from the top of the container to the bottom. After this settling period the suspension was decanted from the settled solids. The settled solids were redispersed in water and the separation was repeated once. The two fine fractions were then combined. Thus the clay was divided into a fine and a coarse fraction by size separation at approximately 2.5 microns.* The fine fractioh was found to have a considerably lower sand content than the raw clay (Table I), and was not treated further. The coarse fraction formed the flotation feed for all the tests described in this paper. A size separation of this type can be

Jan 1, 1947