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By J. B. Gayle

PRESENT flotation processes depend almost entirely on the buoyant properties of air bubbles to effect separations of mineral and gangue, but there is no convenient method for measuring aeration in flotation cells. Consequently the relation between aeration and cell performance has not been definitely established. In connection with a comparative study of kerosene and froth flotation processes, a modification of the displacement method' was developed in which air escaping from the cell surface is measured with a wet-test meter. The arrangement shown in Fig. 1 is satisfactory for use with a number of cells and is not critical, except that care must be taken to use connections and tubing large enough to avoid excessive back pressures. Attempts to use smaller tubing resulted in back pressures that caused displacement of the liquid level in the receiver, so that some air was lost around the sides, an occurrence readily visible when measurements were taken with only water passing through the cell. With the arrangement shown, the manometer indicated an average reading of about 1/2-in. water pressure. No loss of air was evident. Fig. 2 presents typical data for a standard Denver sub-A 24x24-in. unit cell operated at impeller speeds from 0 to 710 rpm. Each plotted point represents the average for five readings distributed over the entire cell surface. Readings were taken with only water passing through the cell. Results of this type have been used in a study of the influence of operating variables on cell performance and in detecting inherent differences in the operating characteristics of cells of various kinds. Although the information presented in Fig. 2 resulted only with water passing through the cell, the apparatus is suitable for use during flotation of coal when various reagents are present. Possible modi- fications that might prove convenient under special circumstances include varying the size and shape of the receiver and substituting a calibrated, inverted, water-filled carboy or other gas-measuring device for the wet-test meter. If such modifications result in excessive back pressures, some form of draft should be applied at the discharge end of the measuring system.

Jan 1, 1959

By M. N. Brodie, John Chapman

INTRODUCTION - DEFINITION & HISTORICAL PERSPECTIVE While this symposium is concerned with comminution which, by definition, relates to all stages of size reduction of an ore body to a form suitable for mineral separation, the electrical drive aspect of the grinding section will receive most attention in contrast to the crushing, screening and materials handling elements of the process. The reason for this is that today's large mills, thirty feet diameter and upwards, present mechanical and electrical problems which require a degree of sophistication in their solution not previously required. The ability to satisfy these demands, so far as electrical technology is concerned, largely results from the development of semi-conductor devices. These can now handle typical electrical distribution power levels within remarkably s m all volumes and with high efficiency when compared with the motor-generator sets, mercury arc rectifiers, rotating amplifiers, magnetic amplifiers and vacuum tubes which were commonly used to provide speed and torque controls as recently as the early nineteen-sixties. The hardware available to the electrical engineer has changed dramatically whereby even the simplest control system formerly using hard-wired relays is now superseded by the program m able logic controller with its computer-like memory containing the sequence of operation, in other words, the software. Reverting now to the mineral process itself, it is assumed that the ore body has been mined using explosives and is delivered to the concentrating plant in its 'run of mine' form. The problem becomes one of reducing the material to a size which will permit an acceptable recovery of the mineral with the most economical use of energy. The size of 'run of mine' material will range from about minus five feet for high tonnage open pit operations to minus two feet for the smaller underground mine. The final reduction in size may range from minus ten mesh to minus two hundred mesh (exceptionally as fine as minus six hundred mesh) depending upon the concentration method and dissemination of the mineral values within the ore. There is no single circuit that satisfies all applications, but the pattern of metallurgical equipment use shown in Table 1 appears discernable from current practice, in general terms.

Jan 1, 1982

By Thomas Leonard Watson

I. HISTORICAL. BARITE has been mined for many years in various parts of Virginia, probably the earliest mining-operations being in Prince William county, within 600 ft. of the Fauquier county line, about 4 miles south of east from Catlett, a station on the Southern Railway. It is claimed that the mineral was mined here as early as 1845. Mining-operations in Campbell and Pittsylvania counties in the Piedmont region, and near Marion in Smyth county, in the southwest Virginia Valley region, were begun about 30 years ago. The mining and milling of barite on a commercial scale in Tazewell and Russell counties are more recent, and commenced about 15 years ago. II. GEOGRAPHICAL AND GEOLOGICAL DISTRIBUTION. Barite occurs in many counties in the State, as shown in Fig. 1, but the industry has been confined to only a few of them. Its occurrence is noted in two of the three major divisions of the State-namely, the Piedmont region east of the Blue Ridge, and the Paleozoic area west of the Blue Ridge. In the Piedmont region the mineral has been mined in the following counties:, Bedford, Campbell, Louisa, Prince William, and Pittsylvania. In the region west of the Blue Ridge, composed of Paleozoic sediments, barite has been mined in Montgomery, Russell, Smyth, and Tazewell counties. Of the counties mentioned, Bedford, Campbell, and Pittsylvania of the Piedmont region, and Russell, Smyth, and Tazewell of the Valley region, have been the principal producers. In 1906, operations were confined to five counties-Bedford, Louisa, Pittsylvania, Russell, and Tazewell-but in the first two counties named there was no production, the work being solely development.

Jan 9, 1907

By J. Jones-Parra, R. S. Reytor

The porosities of fractured limestone reservoirs can be divided into two broad types in accordance with their effects on fluid distribution and fluid flow. In the coarse porosity, gravity segregation lakes place freely and the resistance to fluid flow is very small. In the fine porosity there is no segregation and a high resistance to flow, and it has relative permeability characteristics similar to tight sandstones. By analyzing the affect of the two porosities it is concluded that in some cases to recover the maximum amount of oil it is necessary to remove large quantities of gas from the reservoir by producing at high gas-oil ratios. In this manner the fine porosity is drained of its oil and the gas-oil contact drops slowly permitting higher production rates from the oil leg. Since this conclusion is contrary to widely accepted principles of conservation, a mathematical model (Fig. I) was constructed to duplicate the conditions desired. The behavior of the model indicates that under certain conditions it is possible to recover more oil by producing at high gas-oil ratios than by production at low gas-oil ratios, and that the rate of production is affected more by gas shut-offs than by the decrease in pressure (Figs. 2, 3, 4 and 5). INTRODUCTION It has been noted that certain limestone reservoirs behave in such a way as to indicate that there are two distinct types of porous spaces available for fluid storage and fluid flow. Regardless of the nature of these porous spaces the distinguishing characteristic is that in one type of porous space there is definite gravity segregation between the oil and the gas; while in the other, the gas evolved tends to remain distributed equally throughout the reservoir. For the sake of simplicity the porosity in which gravity segregation takes place at a fast enough rate to affect the behavior will be called "coarse po- rosity", while that in which this is not so will be termed "fine porosity". The behavior of a reservoir of this type would be different than that of a sandstone reservoir, especially if most of the oil is in the fine porosity. It has been observed that fluid flow to the wells takes place mostly through the coarse porosity. The large fractures which

By W. A. Hockings, D. W. Fuerstenau, A. L. Mular

This paper briefly describes a simple air pycno-meter and its use for rapid determination of the composition of mixtures of solid particles. Research on such problems as the pelletizing of solids, the mixing of solid particles, and the comminution of mixtures can be simplified by means of this analytical tool. THEORY OF OPERATION Liquid pycnometers1 are commonly employed to measure volumes. These devices are time consuming and sometimes give inconsistent results. The liquid used in the pycnometer may have an undesired influence on the material to be measured; moreover, complete displacement of air by the liquid is seldom

Jan 1, 1963

By Michael S. Koleda

Less than two years ago, the, Congress, with broad bipartisan support, passed the Energy Security Act of 1980. A decade marked by ten- fold increases in world oil prices and two major interruptions in oil flows from the Middle East had ended. An all-out national commitment to transform America's vast tar sands, oil shale and coal resources into conventional fuels had begun. The national synfuels effort was to be public-private cooperation at a scale unmatched in peace time. Private industry would own and operate the synthetic fuels facilities. Government would reduce market uncertainties to acceptable levels. The potential government commitment was substantial. Up to $88 billion would be available through the Synthetic Fuels Corporation, principally in the form of contingent financing. Billions more would be spent through Department of Energy programs. Additional incentives for alternate energy development were contained in the Energy Tax Act of 1978. The Energy Security Act clearly specified national synthetic fuels production objectives: 500,000 barrels per day by 1987 -- 2 million barrels per day by 1992. Finally, said Congress, Uncle Sam was going to do something about rapidly rising oil prices, uncertainties of energy supply, and the resulting disruption to the U. S. economy. Simply put, the purpose of the Energy Security Act of 1980 was to provide government guarantees sufficient to get synthetic fuels projects off the private sector drawing boards and into commercial production. Because of their huge cost, technological uncertainty, and lengthy pay-out period, these projects were always second place to projects of smaller size, known technology and more rapid pay-out. The Energy Security Act was the legal expression of public policy to bring the free-market synfuels timetable into line with the faster paced political timetable in the interest of national energy security.

Jan 1, 1982

By H. J. Modi, D. W. Fuerstenau

pH effectively regulates the flotation of corundum through its control of the surface charge. Since collector ions function as counter ions in the double layer, the collector must be anionic when corundum is positively charged and cationic when it is negatively charged. Even a long-chained xanthate will float positively charged corundum. Association of the hydrocarbon chains of the adsorbed collector ions gives rise to increased adsorption and increased rate of flotation. Because of this phenomenon, neutral organic molecules aid flotation although the unionized collector cannot promote flotation independently. Na2SO4 was found to depress the flotation of corundum with animic collectors through ionic competition whereas the same salt activates corundum for flotation with cationic collectors. A close connection between ion association, electrokinetic behavior, and floatability is suggested. As part of the increasing interest in the physical chemistry of flotation, strong experimental evidence has been obtained which indicates that organic ions are adsorbed as counter ions by non-metallic oxide minerals mainly because of the electrical forces which exist at interfaces(1-3). Thus flotation of such minerals without activation should then be appreciable only when the mineral and the collector are oppositely charged. Since only limited work has been reported on the effect of surface charge upon flotation behavior(3) this general hypothesis on the flotation of insoluble oxide minerals has not been tested thoroughly. Investigating the flotation of a mineral for which extensive electrokinetic data exist yields a way to test this hypothesis more extensively. The electrokinetic behavior of corundum in solutions containing both organic and inorganic electrolytes has been studied quite thoroughly' Electro-kinetic measurements have shown that in the case of corundum, simply by controlling pH the solid surface can be charged either positively or negatively. For this reason corundum was chosen for study. The object of this paper is to present a study of the flotation of corundum and to explain the results in the light of our knowledge of adsorption mechanisms gained from streaming potential investigations. This paper is concerned mainly with the effect of surface charge on flotation with anionic and cationic collectors, but in addition such flotation phenomena as collector hydrolysis, Van der Waals attraction between hydrocarbon chains, ionic competition, and activation are discussed. While the present paper is confined to a reporting of the data obtained and some of the more immediate conclusions, it will be seen that the results, in combination with those on other systems, do promise a

Jan 1, 1961

By V. H. Whihelm

Since 1935 California has enjoyed a remarkable cycle of discovery, which has placed the state in a very satisfactory position in regard to oil reserves. Most ol the geophysical plays have been drilled and it is possible that new discoveries must be made by the application of careful geologic and stratigraphic studies. During 1940 only one new field was discovered, which, although not of major importance, may lead to additional discoveries. During the year, 113 wildcats were drilled. New discoveries, extensions and a reappraisal of discoveries made in 1939 will not approximate over 50,000,000 bbl., as against an estimated withdrawal during the year of 224,000,000 barrels. Demand in terms of crude for 1940 was 632,000 bbl. per day as against 626,000 bbl. per day for 1939. Demand for gasoline was the same as in 1939, but the demand lor fuel oil increased 3.8 per cent. Compared with 1939, Japanese shipments decreased from 75,786 bbl, per day to 61,000 bbl. per day, but the balance of Pacific foreign shipments increased from 59,409 bbl. per day to 61,304. Total with-drawals from storage during the year will approximate 7,000,000 bbl., almost all of which is fuel oil. Drilling activity was slightly greater than in 1939 and accounted for 890 new producing wells as against 851 for 1939 (Table 3). Production averaged 611,900 bbl. per day as compared with 614.,842 bbl. per day for 1939. The productive acreage figure of the state was increased by 4000 through discoveries and extensions. New Discoveries Los Angeles Basin District Del Vdle Field.—Northwest of Newhall, where the first oil well in California was drilled, R. E. Havenstrite completed his Lincoln No. I well, flowing 390 bbl. of 50" gravity oil together with 7000 M CU. ft. of gas. Later the well was recompleted, after cutting off the gas, for 950 bbl. of 34" gravity oil. The type of structure from which this production is coming is a plunging anticline, complicated by faulting. The Lincoln No. I well uncovered approximately 180 ft. of net sand. This field contains a gas cap and its indicated productive area approximates 500 acres. An intensive wildcat drilling campaign is expected during this coming year in the district in the vicinity of the Del Valle field. Extensions and Deeper Sand Developments Los Ange1es Basin District Athens Field.—On the northwest plunge of the Athens structure, the Thorley Oil Co. completed its No. 12-1 well, flowing 250 bbl. of 3 2" gravity oil from a depth of 8097 ft. The area in which the well is located is complicated by faulting and it is impossible at this date to determine the importance of this deep-zone discovery.

Jan 1, 1941

By V. H. Whihelm

Since 1935 California has enjoyed a remarkable cycle of discovery, which has placed the state in a very satisfactory position in regard to oil reserves. Most ol the geophysical plays have been drilled and it is possible that new discoveries must be made by the application of careful geologic and stratigraphic studies. During 1940 only one new field was discovered, which, although not of major importance, may lead to additional discoveries. During the year, 113 wildcats were drilled. New discoveries, extensions and a reappraisal of discoveries made in 1939 will not approximate over 50,000,000 bbl., as against an estimated withdrawal during the year of 224,000,000 barrels. Demand in terms of crude for 1940 was 632,000 bbl. per day as against 626,000 bbl. per day for 1939. Demand for gasoline was the same as in 1939, but the demand lor fuel oil increased 3.8 per cent. Compared with 1939, Japanese shipments decreased from 75,786 bbl, per day to 61,000 bbl. per day, but the balance of Pacific foreign shipments increased from 59,409 bbl. per day to 61,304. Total with-drawals from storage during the year will approximate 7,000,000 bbl., almost all of which is fuel oil. Drilling activity was slightly greater than in 1939 and accounted for 890 new producing wells as against 851 for 1939 (Table 3). Production averaged 611,900 bbl. per day as compared with 614.,842 bbl. per day for 1939. The productive acreage figure of the state was increased by 4000 through discoveries and extensions. New Discoveries Los Angeles Basin District Del Vdle Field.—Northwest of Newhall, where the first oil well in California was drilled, R. E. Havenstrite completed his Lincoln No. I well, flowing 390 bbl. of 50" gravity oil together with 7000 M CU. ft. of gas. Later the well was recompleted, after cutting off the gas, for 950 bbl. of 34" gravity oil. The type of structure from which this production is coming is a plunging anticline, complicated by faulting. The Lincoln No. I well uncovered approximately 180 ft. of net sand. This field contains a gas cap and its indicated productive area approximates 500 acres. An intensive wildcat drilling campaign is expected during this coming year in the district in the vicinity of the Del Valle field. Extensions and Deeper Sand Developments Los Ange1es Basin District Athens Field.—On the northwest plunge of the Athens structure, the Thorley Oil Co. completed its No. 12-1 well, flowing 250 bbl. of 3 2" gravity oil from a depth of 8097 ft. The area in which the well is located is complicated by faulting and it is impossible at this date to determine the importance of this deep-zone discovery.

Jan 1, 1941

By J. Gordon Parr, D. H. Polonis

IN a previous study of hypereutectoid Ti-Ni alloys' a substructure was observed in quenched powder specimens when the constitution was 100 pet retained ß body-centered-cubic phase. The alloy powders were quenched from 1000°C by a blast of helium gas and precautions already described were observed throughout the work, to minimize contamination. Ogden et al.2 have previously observed subboundaries in the ß phase of a Ti-Mn-N alloy; but this structure was attributed to nitrogen-rich a precipitation. The nitrogen content of the Ti-Ni alloys does not exceed 0.02 pet and the quenching rate was sufficiently rapid to suppress precipitation reactions. Since X-ray diffraction results have confirmed the absence of any second phase which might account for this phenomenon, it seems unlikely that this substructure is explicable in terms of nitrogen content. Fig. 1 shows the substructure in adjacent grains of 100 pet ß phase in a quenched 6 atomic pet Ni alloy. Fig. 2 shows adjacent ß grains in a similarly treated alloy; one grain contains marked intracrys-talline boundaries and the other is completely free from any substructure. The suberystals appear to have fairly regular shapes, suggesting a regular orientation relationship among them. Tempering the retained ß structure at temperatures below the eutectoid eliminates the substructure at an early stage of ß decomposition. At the present time it is possible only to guess at an explanation for this subboundary phenomenon, since very little work has been reported on substructures resulting from phase changes. It is believed that the present phenomenon is due to poly-gonization resulting from unrelieved stresses set up

Jan 1, 1957

By H. Morgolin, M. A. Greenfield, P. A. Farrar

In attempts to correlate mechanical properties with microstructure, it is desirable to determine the effect of ß grain size. Determination of 6 grain size is not a problem where a has precipitated at ß grain boundaries. However, in alloys which have been processed to produce an equiaxed a +ß structure the ß grain size is difficult to determine because ß grain boundaries do not etch. The ß grain size can sometimes be laboriously determined by searching for grains which have some a! outlining the 6 grains. This difficulty of ß grain size determination in equiaxed a + ß alloys can be overcome by heating below the ß transus temperature for a short time and water quenching. Fig. 1 shows the starting equiaxed a + ß structure of the Ti-5.25A1-5.5V-0.9Fe-0.5Cu alloy used in this investigation, and Fig. 2 shows the microstructure of the same sample water-quenched after heating 1 min at 1675"F, which is 25°F below the 0 transus. The heavily etched microstructure consists of some equiaxed a! in a structure showing considerable amounts of transformed ß. The ß grain

Jan 1, 1969

By Sherwin F. Kelly

Twenty five years of exploration has shown that the "geophysical dollar" is worth $1780 in the Orange Free State, $1488 on the Witwatersrand, $85 in Sweden, $28,000 in the Transvaal and $3500 or more in the U.S.

Jan 6, 1951

By A. H. Larson, L. G. Twidwell

DURING the roasting of zinc sulfide concentrates and by-product recovery from flue dusts, the zinc sul-fate phase may occur in various stages of the processes. In addition to zinc sulfide, other sulfide phases are usually present such as CdS, PbS, CuzS, and FeS. Consequently, the effect of these sulfides on the thermal decomposition of ZnS04 was investigated. Merck high-purity, anhydrous zinc sulfate was used as the starting material. The sulfate was heated under an argon atmosphere, at a rate of 10°C per min. With the first slight indication of decomposition as determined by gas analysis, the sample was removed from the furnace and allowed to cool. X-ray patterns showed no other phase present. It is estimated that less than 0.05 pct of the ZnS04 decomposed. The metal sulfides were also heated under an argon atmosphere to drive off any adsorbed water. The materials were then sized (-200 to +270 mesh), mixed in predetermined mole ratios, and pressed into pellets. The experimental measurement of the reaction rate consisted of purifying the argon carrier gas, continuous flushing of the heated reacting mixture with argon, and collection and analysis of the SOn product gas. The reaction system was heated to 600°C and al-

Jan 1, 1967

By Eugene McAuliffe

AS this is written, the probability A is that the bituminous coal out- put for 1936 will approximate 420,000,000 tons (of 2000 lb.) with an average working time for all mines of 205 days. The results for 1935 approximated 369,224,000 tons, with the mines working about 185 days. The increase in production of 14 per cent is heartening. In anthracite, it is probable that the preliminary figures covering output for 1935, 51,- 003,000 tons, will be exceeded this year although the percentage of in- crease will almost certainly be small. The substantial tonnage of anthracite illegally mined, estimated to be 3,600,- 000 tons in 1935, with a similar large Lonnage in 1936, is in addition to the figure given above; it represents an open and flagrant disregard of law and property rights. It is hard to understand why the officials of the State of Pennsylvania do not enforce the laws against theft and brigandage, more so when the legitimate employees of the established producing proper-

Jan 1, 1937

By N. A. Gjostein

From their study of the anisotropy of grain boundary mobility in aluminum, the authors conclude that tilt boundaries have a higher mobility than twist boundaries because the atomic misfit at the pure-twist boundary is relatively small compared to the misfit at a tilt boundary for a given amount of misorientation. If this is true, then one would expect a twist boundary to have a lower grain boundary energy than the corresponding tilt boundary. Fig. 6, taken from the work of Gjostein and Rhines,10 shows that this is indeed the case for [001]-cu tilt and twist boundaries in the high-angle region, thus lending support to the authors' conclusion.

Jan 1, 1968

By W. V. Long, D. H. Reynolds, R. B. Bhappu

Equilibrium distribution coefficients were determined for some monovalent and polyvalent ions for several absorbing and exchanging media as functions of pH and initial ion concentration. Among ions studied were NH4 (I), K(I), Ni(II), Ce(III), Th(IV), and Mo(VI). Absorbents used were: ion exchange resins; a tertiary, and a quaternary amine in an inert solvent; and some activated carbons. The ions studied were in aqueous HCI, HNO3, H2SO4, or HC104 solutions. The classical mass action expression proved of little value in describing the variations observed. The data indicate that the determining factors in absorption and ion exchange may be the ionic species in the aqueous solution, which in turn depend upon pH, dilution, and perhaps other conditions. Three sorption processes have become prominent in recovering values from leach solutions. These are: 1) ion exchange, 2) solvent extraction (liquid ion exchange), and 3) physical adsorption by materials of high specific surface. In the first two of these processes the exchange reaction is considered chemical in nature, and is discussed in terms of the mass action principle. The third is considered a surface phenomenon and is discussed in terms of surface areas and various forms (Gouy, Stern, Grahame, etc.) of the Helmholtz double-layer theory. Generally speaking, we have found in chemical analysis and hydrometallurgical studies that there are close similarities between the three sorption processes, and also differences which are difficult to reconcile with any of the usual theoretical treatments. That others have experienced the same troubles is shown by the fact that usable processes, in chemical analysis as well as in hydrometallurgy, generally are discovered by empirical procedures. EXPERIMENTAL CONSlDERATlONS The gaps between theory and practice have allowed many conflicting statements to appear in the litera- ture. To learn, in particular, the behavior of some metallic ions on a cation exchange resin at a constant pH, equilibration studies were made over a wide range of concentrations.' Results are shown in Fig. 1 for four metals in hydrochloric acid solution on a strongly acidic cation exchange resin, AG 50W-X8 (Bio-Rad). The distribution coefficient, defined as D = amount of metal extracted per g of resin/amount of metal unextracted per ml of solution is seen to vary in a way to support all manner of reports about its behavior with changes in solution concentration. The metals used were chosen from those least likely to form stable chloro-complexes. The changes of slope in the various isotherms may reflect formation of unsuspected chloro-complexes of low stability (ion-pairing for example) whose concen-

Jan 1, 1967

By R. Gilman Brown

INTRODUCTION. MINES are interesting by reason of what they have done for man, or of what has been done for them by nature. Not all are interesting on both scores. Many profitable mines are commonplace to the geologist; and many presenting unique geological conditions have been sad failures commercially. The Standard group at Bodie has produced in 25 years, $14,500,000, paying $5,000,000 in dividends.' On the other hand, this output has been mined (almost wholly above the 1,000-ft. level) from a system of more than 100 veins, ranging in thickness-from 0.5 in. of "specimen rock" to 30 ft. of clay and quartz; distributed through a zone about 2,000" ft. in width, and representing from three to five distinct periods of formation. This group, therefore, by reason of its industrial record as well as its geological features, may fairly be regarded as doubly interesting. The Bodie district occupies an island of recent (Tertiary) hornblende-andesite, surrounded by a complex of igneous rocks and breccias. It lies at the summit of the eastern foot-hills of the Sierra Nevada mountains, and within the Great Basin, a few miles from its western edge, marked here by Mono lake on the line of the Great Fault. The average elevation of the outcroppings of the veins may be taken at about 5,700 ft. The andesite projects from south to north in a great tongue, 12,000 ft. long and 5,000 ft. wide, reaching an extreme height at the northern end of perhaps 1,000 ft. above the adjoining small canyons. These separate it from the main mass of the foot-hill

Jul 1, 1907

By Charles E. Heinrichs

IN the last decade one of our oldest and largest non-metallic metallic mineral industries has been the subject of persistent technical research, the results of which are another example of the benefits following the systematic application of scientific principles. The consequent improvement in the technique of phosphate recovery represents the greatest material advance in the industry since the discovery of phosphate in Florida in 1881. Moreover, these successes have stimulated interest and development in numerous other nonmetallic industries. Strange as it may seem, and despite the fact that the phosphate deposits of Giles County, Tennessee, together with those of Polk and Hillsborough Counties, Florida, have yielded more than 50,000,000 long tons in the last twenty years, the mineralogy of phosphates has been given scarcely any space in our technical literature. For many years it was the general consensus that these so-called phosphate rocks represented a physical mixture composed principally of tri-calcium phosphate, together with smaller quantities of calcium carbonate, calcium fluoride, iron phosphate, aluminum phosphate and other less important constituents. More recent investigations, however, led to the conclusion that these phosphates really represent a complex mineral in which calcium, iron, aluminum, phosphorus pentoxide, carbon dioxide, and fluorine all form a definite part of the molecule. Colony, after a careful study, utilizing chemical, microscopic, and X-ray diffraction methods, reported that American phosphates consist principally of calcium-carbono-phosphate of the staffalite type.

Jan 1, 1933

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

Discussion of the paper of Robert Henry Lee, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2515 to 2522. J. E. JOHNSON, JR., New York, N. Y.:-This subject is of great and increasing importance, as the exhaustion of the deposits of ore of ideal character compels the iron industry to turn more and more to those which are less desirable on account of physical structure as well as analysis. Thus there has come about the use of the Mesabi ores in this country and also of the Minette ores in Europe, which produce far greater percentages of flue dust than did the lumpy ores first used. It is a matter of common knowledge that the utilization of this flue dust, containing commonly 50 per. cent. or more of metallic iron, has been a problem very difficult and tedious of solution. The number and variety of the solutions now offered is a sufficient proof of this. . I have no intention of going into the merits or demerits of any of these processes as such, but there are certain considerations concerning the effect of their product on the operation and fuel economy of the blast furnace which I believe to be new and which I desire to bring out. There are two methods, so different as almost to be direct opposites of each other, whereby an ore may exercise an unfavorable effect on the economy of the blast furnace. The first of these is well known and results from the ore being refractory and highly resistant to the action of the reducing gases of the blast furnace. This results in its being incompletely reduced when it reaches the zone of fusion and in the reduction being finished by the direct action of carbon in the lower portion of the furnace. This is so well understood as to need little elaboration or comment. There is, however, another action which may be equally as fatal to the economy of the furnace as the foregoing, and as this point is, to the best of my knowledge, not generally appreciated, it is one upon which I desire to lay particular stress. This consists in the ore being, in a sense, too reducible.

Jan 12, 1913