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By Charles A. Ashburner

' I. Natural-Gas Explorations. The rapid development of the natural-gas* industry in Western Pennsylvania, and the great economy which results from its use, both for manufacturing and domestic purposes, has led to an inquiry as to the occurrence of this gaseous mineral in all thickly populated and large manufacturing centers of the United States. Natural-gas springs are to be found in almost every State in the Union, and in many States gas has been obtained in wells sunk either for water, oil, or gas, or in search of solid mineral deposits. The occurrence of natural gas is, however, not dependent upon mere chance, as is popularly supposed, but upon the existence of special geological phenomena; this fact is now recognized by professional men and by many practical men concerned either in the exploration for or in the use of this gas. The desire among our leading manufacturers, to emulate Pittsburgh, has led to the sinking of many wells in many localities, in search of natural gas. Some of these wells are now being located and drilled under the direction of professional experts, but many more have been, and are still being located by "quack " explorers, who often depend upon spiritualistic communications, or the diviningrod, or by intelligent persons, who are ignorant, however, of the geological and physical conditions under which gas has already been found. My attention has recently been directed to a number of these exploring operations where holes have been drilled, and, after failing

Jan 1, 1887

By H. T. Hildage

ALTHOUGH Greater New York does not bear any resemblance to a great mining district, the mining operations that are being conducted in and about the city are both extensive and interesting in character. With regard to the extent, it may be mentioned that, at. present, there is more dynamite used in New York than in any mining district in the United States; that there are under construction about 38 miles of tunnel, and that 66 miles more are projected, most of which must be constructed in the near future ; that since 1902 at least 2,000,000 tons of earth has been removed in underground work, in addition to about 3,500,000 tons that has been removed in, open-cut in connection with tunnel-work, and many times this quantity that has been removed in excavating foundations for buildings not connected with tunnel-work; and that there are to-day probably more than 5,000 men engaged in mining-work in and about New York City. These undertakings include almost every operation connected with underground work, from exploration by means of trench and boring, to the sinking of large shafts and the driving of large tunnels through every kind of ground from hard rock to soft, semi-fluid silt and quicksand. It is proposed in this paper to give a general description of some of the methods and appliances used in the opening-up ,of a "mine" in a large city, and a brief description of some of the "mines" now being developed in New York, connecting as far as possible the methods described with the particular work for which they were designed, in order to give a general idea of the

May 1, 1907

By Henry C. Freeman

During the early period of the construction of the Illinois and Michigan Canal, about 1838, in excavating for the canal, where the present town of Utica stands, hydraulic limestone was discovered, and its value was recognized. A kiln for calcining and a mill for grinding were erected, and the cement was used in the construction of the locks of the canal. This property was subsequently bought by the present owner, Mr. James Clark, and the work has been continued to the present time in much the same primitive manner as it was begun. The bed is exposed in the Illinois River valley by stripping off a few feet of the covering rock. It is from 4 feet to 6 feet 9 inches thick, and nearly level, dipping gently to the northeast. The Utica Cement Company's establishment, which is two miles west of Utica and two miles east of La Salle, was an outgrowth of the Illinois geological survey. The writer was in charge of the district which included La Salle county, and, in working out the details of the geology of that county, discovered, below the Utica bed, another workable hydraulic limestone, which makes its appearance in the northern bluff of the Illinois River valley, rising above the water level at the point where the company's works are established. This cement group, of which there are several thin beds, lies just below the St. Peter's sandstone, with a few feet intermediate of transition-rock, which appears to represent the Calciferous, and is exhibited in place, in concretionary form, at the top of the bluff. The hydraulic beds are very regular, and the one worked by the company is 10 feet thick; or, speaking more definitely, there are two beds, separated by 18 inches of sandstone, lying about two feet above the bottom, and the two beds are worked as one, the sandstone being first cut out and removed, to prevent mixture. In 1869 I was invited to join with a company, and to take charge

Jan 1, 1885

By E. N. Harshman

The Wind River Formation of Eocene age is the host rock for large high-grade uranium deposits in the Shirley Basin. The major deposits are in a northwest-trending belt of sandstones that were deposited in stream channels and that were lithologically favorable for uranium accumulation. Paleotopography influenced the character and position of the belt. The major deposits within the belt are at, or near, the margins of large tongues of altered sandstone formed in the most transmissive parts of thick sandstone beds. At least two tongues of altered sandstone are present in the belt, one of which is 5 miles long, 3 miles wide, and 70 feet thick; the other tongue is somewhat smaller. Ore bodies consist of a few hundred tons to several hundred thousand tons of material containing from 0.10 to about 2.00 per cent U3O8. The ore mineral is uraninite associated with pyrite, marcasite, hematite, and calcite. Deposition is believed to have taken place when neutral to slightly alkaline, oxidizing, uranium-bearing ground water, on entering the basin, encountered a reducing environment. The reductant may have been H2S of biogenic origin. Geology played an important role in discovery, exploration, and development of ore in the Shirley Basin.

Jan 1, 1968

By C. A. Zapffe

BOTH the foundryman and the theoretical metallurgist are now generally agreed that the anomalous "rising" or "bleeding" of certain ferrous castings of killed metal is primarily attributable to hydrogen. How and why the phenomenon occurs, however, have not been made clear. The following discussion is intended to harmonize foundry experience with metallurgical theory so that the foundryman may possibly improve his ability to prognosticate whether a certain casting may bleed or not. BLEEDING, RISING, AND PIPING The "rising" to be discussed here is not to be confused with the action in rimming ingots as a result of the carbon-oxygen reaction, although a conclusion will be drawn that may apply to the art of controlling the rimming action. Only killed metal is considered, which includes both steels and irons. In Fig. I, three killed, chill-cast ingots are shown: a porous ingot whose evolution of gas during late stages of solidification has ejected metal through the top; an ingot in which moderate gas evolution during solidification has lifted the mushy central metal, i.e., it has "risen"; and, third, a sound ingot with good piping characteristics. The first type is referred to as "bleeding," and generally infers that a solid skin had first formed through which the liquid metal later erupted. There is no fundamental distinction between bleeding and rising in reference to killed metal.* POROSITY Hydrogen appears as a cause of bleeding because the gas evolution simultaneously leaves a porosity of a type traceable to hydrogen. Twenty years ago, Melmoth1 noted that killed steel that rose unexpectedly in the mold, if returned while liquid to the furnace and heated further under a reducing lime slag, would again rise in the mold; but that if the ingot were allowed to solidify and was then remelted no rising occurred. A critical quantity of the responsible gas is therefore removed by the rising action. Melmoth associated rising with high silicon (0.7 to 0.9 per cent) and concluded that silicon increased gas absorption. Because silicon is a strong deoxidizer, oxygen must, therefore, be eliminated from consideration of the three common gases in steel-oxygen, nitrogen, and hydrogen. Butterworth2 later decided that pinhole porosity was caused by gases dissolved in the metal and that hydrogen was obtained from steam in the mold. Allen's classical work on copper castings,3 soon followed by

Jan 1, 1942

By Erminio Ferraris

The development of the mining industry in Sardinia dates from the application of the mining law of 1859, which, following the example of the French mining law of 1810, declared prospecting to be free, and suppressed the liens which had previously attached the mine to surface ownership. The first ore-dressing plants were installed by German engineers upon the classic models of the Harz and of Freiberg; but in 1880 Sardinia commenced to open a new path in that industry, utilizing the refuse from the mining of rich, selected minerals, of poor deposits, and of mixed ores. The first experiments were attempte to adapt the existing apparatus to local conditions, but progress was rapid, as was demonstrated already in 1887 by the calamine-dressing mill of Monte-poni, which exhibited a large plant designed in accordance with the experience gained, and constructed entirely in the machine-shops of the country, after new models and designs.' This example was followed two years later by the Sociékté Malfidano, with a large plant of the same sort, and with the reconstruction of the old-fashioned dressing-mill, built in 1880 by the Austro-Belgian Company. In 1900, almost all the mines of Sardinia had adopted the new designs, and the island contained 32 concen-trating-works, employing 2,000 h.p. and 1,924 workmen. Since that time, there have been added a large dressing-mill for blende at Gennamari, and two for calamine, at San Giovanni and at Masua, while the establishments at other mines have been enlarged and perfected. For the treatment of intimately mixed ores, a large establishment has been built upon the new

Jan 1, 1909

By B. B. Rath, Hsun Hu, R. S. Cline

FOLLOWING the techniques used by Beck and co-worker~ "~ the characteristics of selective growth in the recrystallization of a zone-refined aluminum single crystal, rolled 80 pct at -78°C in the (110)[112] orientation, have been studied. The material was 99.999+ pct pure. The as-grown crystal had a resistance ratio, R(298°K) /R(4,2°K), of approximately 5000. The method of preparation of the single crystals and the necessary precautions in handling them during rolling in order to avoid recrystallization in locally distorted regions were described in an earlier paper.3 The rolling texture of this zone-refined aluminum crystal is practically identical with that of less pure aluminum crystals rolle! in the same orientation, i.e., a very sharp (110)[112]. Random nuclei were provided by artificial nuclea-tion by abrading one face of the rolled crystal on 600-grit emery paper in a random fashion. The thin layer of disturbed metal recrystallized at room temperature into fine grains almost immediately. An X-ray diffraction pattern was taken from the abraded surface of the crystal, and the relative intensities of the various reflection peaks were compared with those obtained from a powder specimen. As shown in Fig. 1, the relative intensities of the various peaks from the recrystallized layer varied somewhat from experiment to experiment, depending presumably on the abrading technique. However, the texture of the recrystallized layer produced by this method is nearly as random as that of a powder specimen. Fig. 2 shows the texture determined from the "growth side" (face opposite the abraded surface) of the crystal after it was kept at room temperature for 100 hr. The specimen was only partially recrystallized, as shown by the remaining deformation texture. The new orientations are derived from the recrystallized grains grown through the thickness of the crystal from the "nucleation side" (the abraded surface). Fig. 3 shows the texture after complete recrystallization produced by annealing at 60°C for 1 hr. The arrows indicate 40-deg rotation around the (111) axes of the deformation texture. The microstructure of a completely recrystallized specimen is shown in Fig. 4. As shown in Figs. 2 and 3, the texture of the re-crystallized grains grown from the nucleation side to the growth side is essentially the same as that observed in less pure aluminum' (99.994 pct) and dilute alloyz crystals rolled in the same orientation. How-

Jan 1, 1968

By W. P. Haynes

ESTIMATED United States crude-oil production during 1943 established a new annual peak of 1,500,000,000 barrels, a daily average of 4,118,000 barrels. This would be an increase of 315,000 barrels per day, or 8 per cent over 1942 and 7 per cent over 1941, the previous peak. During the first ten months of the year, production jumped from 3,782,000 barrels per day in January to 4,400,000 in October. Available data for the last two months of the year indicate a leveling off of this trend, with daily rates slightly above 4,400,000 barrels.

Jan 1, 1944

By Open-Hearth Steel

We have a very high-powered organization up here this morning, headed by Kenneth C. McCutcheon, general superintendent of the Ashland Division of the American Rolling Mill Company, and L. A. Lambing, superintendent of the open-hearth and Bessemer departments of Jones & Laughlin Steel .corporation of Aliquippa, Pa., representing the open-hearth men. Also, we have P. F. Dolan, assistant general manager of the Maryland plant of Bethlehem Steel Company, of Sparrows Point, and Harry E. McDonnell, superintendent of blast furnaces of Weirton Steel Company of Weirton, W. Va., representing the blast-furnace section.

Jan 1, 1940

By H. C. Schultz

CERTAIN local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to usefully develop its full disruptive effect in hard ground. The individual blasts at Chuquicamata are large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with L. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast.

Jan 1, 1928

By Sidney A. Swensrud

Much has been said and written about uneconomic and evil marketing practices in the oil industry, including such factors as loaning of equipment, price cutting and secret prices, commercial discounts, abuses of credit cards and coupon books, and so forth. It is not my purpose here to add to the discussion of those problems, but rather to attempt a discussion of some of the more basic factors in the general distribution economies of the industry. The economics of distribution in the oil industry cannot be regarded apart from the general economics of the industry as a whole. The attempt to regard them as separate has led many people into the fallacy of believing that the responsibility for the apparent evils in the marketing end of the business lay entirely at the door of the marketing end. Such a view fails to take cognizance of many underlying factors; we can only expect to understand the distribution economics of the industry if we understand its general economics. We must realize also that the oil industry today is essentially the gasoline industry. The oil industry may be said to have begun about 60 years ago. At the outset it was concerned chiefly with the manufacture and sale of kerosene, lubricating oils and greases. Gasoline was then a most obnoxious by-product. The early oil-marketing company was engaged almost exclusively in refining and marketing—it did not concern itself with production but bore the relation to it merely of a purchaser. It may be said that the urge of marketing development in those days, therefore, came from the refining and marketing end of the business. The raw material had not yet begun to exert its enormous pressure, nor had the producer of crude oil acquired a direct interest in the sale of the ultimate finished products. Since then great changes have taken place. With the development of the automobile came a vast new demand for the raw material from which gasoline could be made. No longer could the refining and marketing companies be indifferent to the source of that raw material, particularly in view of the pessimistic outlook then presented as to the probable quantity of oil in existence. And despite the complete overturning of those early estimates, made before the bounty of nature and the skill of

Jan 1, 1931

By Paul F. Kerr, Donald M. Hausen

Fine colloidal gold near Carlin, Nevada is disseminated in leached carbonate strata of the Roberts Mountains Formation in the Lynn "window" of the Roberts Mountains thrust fault. The ore body is generally stratiform and is more or less conformable to altered beds near the top of the formation, underlying Devonian limestones. Two sequences of mineralization are recognized: ( 1) an earlier base metal-barite assemblage related to early Cretaceous intrusives (121 ± 5 m.y.), and (2) a later low temperature Au-As-Hg-Sb assemblage of near surface emplacement. The earlier sequence consisting of sparse galena and sphalerite in barite with anomalous amounts of zinc, lead, nickel and copper, associated with dikes of dacitic composition, is of little economic importance. The later sequence of gold, realgar, cinnabar, and stibnite associated with extensive silicification and argillic alteration of limestone beds, has resulted in important deposits of gold. Argillic alteration of hydrothermally leached carbonate strata has provided the environment in which the most prominent gold deposition took place. Carbonate minerals in the limestone host rock have been replaced by microcrystalline quartz and chalcedony to form stratiform silica masses and recrystallized lenses of euhedral quartz. Zones of porous silicification are light gray to white, elliptical in shape, and more or less follow bedding. Silicification is bordered by argillic alteration and pyritization. Deposition of gold usually lies in a zonal pattern that encircles chimney areas of silicification.

Jan 1, 1968

By A. T. Churchman

The deformation modes of rhenium have been identified as those typical of the hexagonal metals, titanium, zirconium, and beryllium whose c/a ratios, in common with rhenium, are less than ideal for close packing. Slip is observed on (1010), (1011), and (0001) planes and twinning on (1121), (1122), and (1012) planes. The very high rate of work hardening is believed to be associated with intersecting partial dislocations on two (1010) systems which can combine to form sessile barriers. If the stacking fault energy is low, as postulated by Seeger, these barriers should be strong and not easily bypassed by cross slipping. Such an explanation could also account for the very small temperature dependence of the yield stress which was observed. RHENIUM is interesting scientifically as a member of the group of high melting point hexagonal metals: titanium, beryllium, and zirconium with a c/a ratio less than that for ideal close packing. Unlike them, however, it work hardens at a very high rate. This rate is greater and continues to a much higher degree of deformation than for nickel, normally considered to have a high rate of work hardening. This paper presents experimental observations on the modes of deformation of rhenium and, by comparison with other hexagonal metals, some speculation on the cause of the high work hardening. MATERIALS Johnson, Matthey rhenium powder of both 99.9 pct and 99.5 pct purity, see Table I, was compacted at 10 tons per sq in., part sintered at 1350°C in vacuo, and finally arc melted in a "gettered" argon atmosphere arc furnace to produce small buttons. Little difference was observed in the as-cast hardness or working down behavior of the two purities suggesting that either silicon and potassium do not have a significant effect on the working properties of rhenium or they were lost during arc melting. SPECIMEN PREPARATION The cast structure was broken up by cold-rolling with inter-stage annealing at 1600o or 1800°C in a vacuum high-frequency furnace using a tungsten susceptor. Strip for tensile testing was taken from two thicknesses of material 0.011 and 0.064 in. The former with intermediate anneals at 1800°C had a grain size of 900 grains per sq mm, while the latter with inter-stage annealing at 1600°C had a grain size of 3600 grains per sq mm. A coarse grain size was obtained by secondary recrystallization in a half button cold-worked by 30 pct reduction. Annealing times of from half an hour to several hours at 2200° to 2600°C in a "gettered" argon atmosphere arc furnace1 resulted in grains of up to 2 mm diam.

Jan 1, 1961

By W. E. D. Stokes

The application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government rccords, 30 Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the railway at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a community of 1000 whites have been transported by airplane. A 31/2-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo. Many large American oil companies operated fleets of planes during 1936, ranging from fast, luxurious air liners for executives to elaborate geological prospecting units, ambulance planes, freight carriers and pipe-line repair crews. According to the U. S. Geological Survey, commercial firms photographed 16,291 square miles during 1935, while the Government compiled from aerial photographs by the Geological Survey in the United States 85,544 square miles. It was found that information could be determined in a fraction of the time required by surface methods. However, sounding a word of caution, a Commonwealth of Australia government report on aerial survey operations had this to say: It is necessary to repeat ad nauseam that aerial photographic survey is in no sense a substitute for geological investigation, though it is a very valuable adjunct thereto, and greatly facilitates and aceeleratcs geological mapping. There are many details

Jan 1, 1937

By William H. Shockley

THERE was an, extensive mining and industrial exploitation of Russia, about 20 years ago, by Belgian, French and British capitalists; but the results were discouraging. It is said that the Belgian and French public together lost approximately $400,000,000, chiefly in the coal and iron industry of southern Russia. This loss is largely accounted for by the fact that most of the companies were formed, as usual in " boom " times, to sell stock; and that thorough investigations were not made. In 1906, renewed interest was taken in Russian mines, especially in those of gold and copper, and a considerable literature is growing on this subject; but as yet I have seen no account of one of the large Russian mining estates. The following notes on such property, where the conditions are so different from those in the mining regions of the United States, should be of interest This inadequate and probably somewhat inaccurate account is made up, partly from my own notes made on the ground, in the summers of 1904 and 1905, and partly from a volume on the geology and resources of the estate issued several years ago, containing surface-and mine-maps, and from a pamphlet published in 1904, giving a general account of the condition and prospects of the property. This pamphlet includes a report made by Arthur L. Pearse, a member of this Institute, in 1899. Both these books are in Russian, and were prepared by the Bogoslovsk Mining Co., which owns and operates the property. Articles in many other languages have appeared dealing with various matters connected with the estate; but I know of no other general account of it. In numerous books and articles on the Urals and Siberia, however, localities are described in which somewhat similar conditions prevail. Recent papers by

Mar 1, 1908

By J. C. Borland, J. H. Rogerson

Jan 1, 1963

By C. S. Harloff, Frank R. Corwin

THE Nichols Copper Co., associated with the Phelps Dodge Corp. and the Calumet & Arizona Mining Co., has constructed at El Paso, Tex., and is now operating a copper refinery with a yearly capacity of 100,000 tons of anodes. Transportation facilities were perhaps the most important of the considerations that led to the selection of this site. The rapid industrial development of the Middle and Far West has increased the consumption of copper there. The advantage of local refining as against shipping the copper to the Atlantic sea- board is apparent. Copper refined in the Southwest is equally competitive for export shipment, either from the Gulf or the Pacific Coast ports. The tonnage of copper produced in the Southwest not only justifies the construction of this plant, but may warrant considerable expansion in years to come.

Jan 1, 1930

By J. B. Mackintosh

The general method which has been followed since the time of Heinrich Rose, and perhaps before, for the determination of phosphorus in iron and steel, is to dissolve the sample either in nitric acid, aqua regia, or some other oxidizing agent, in order to convert the phosphorus into phosphoric acid. In 1832 Rose* recommends HNO3, or aqua regia, preferably the former. Wohler, in 1854,† directs that the iron should be oxidized by burning in a stream of oxygen for the determination of carbon, and the resulting oxide of iron containing all the phosphorus as phosphoric acid be treated as an ore. In the fourth English edition of Fresenius' Quantitative Analysis,† pp. 666-667, we find directions to dissolve the iron in aqua regia or bromine; and, coming down to more recent times, we find F. A. Cairns § directing the employment of a boiling solution of potassium chlorate and hydrochloric acid for the oxidation and solution of the sample to be analyzed. It is unnecessary to multiply quotations from the literature of the subject, though they might be extended almost inclefinitely, since it would only be a repetition of the above mentioned series of methods in one form or another; and the references given have been selected to show how little essential variation there is in the type-methods of solution used. In fact it seems to be universally accepted as a necessary first step in the determination that some such method of solution should be followed. One chemist, however, struck out on a different line of thought, and to the Lest of my knowledge only one, M. V. Tantin, who, in

Jan 1, 1886

By A. B. Kinzel

PRECISE knowledge regarding the effect of heat treatment on the properties of steel has made possible the detailed specifications and instructions covering optimum heat-treating temperatures and practices that are in current use. A distinct contrast is presented by the metal-lurgical treatment of steel adjacent to a fusion weld, as such steel is subjected to each, temperature from room temperature to fusion tempera-ture, and cooled at a rate that is not generally controllable but is pre-determined by the nature of the assembly to be welded, the kind of welding used, and the surrounding conditions. This is true regardless of the type of fusion welding: oxyacetylene, electric arc, thermit or flash resistance. Therefore it seemed desirable to investigate the effect of this metallurgical treatment on the characteristics of carbon steels commonly used for welding, by a detailed study of metal subjected to each temperature range; i.e., each heat-affected zone. Oxyacetylene welding was chosen for the investigation because of the experimental facility of accurately segregating and studying each tem-perature zone. The nature of the zones produced by other types of welding is the same. The difference is primarily a matter of dimensions of each of the temperature zones involved. The advantages and dis-advantages of the extent of the zone are of prime moment, and are dis-cussed after the presentation of the detailed zone study. No mention is made of the fused metal proper, as this has been the subject of much published research and the nature of the solidified metal is fairly well known.

Jan 1, 1935

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971