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By J. B. Campbell, V. V. Valleroy, B. T. Willman, L. W. Powers

A steam drive of heavy oil was field tested in a shallow, low oil-saturation formation near Deerfield, Mo. The pilot was conducted in the Warner formation, a sandstone containing an 18' API oil having 1,000-cp viscosity at the 60F origind reservoir temperature. The formation war at a depth of 160 ft. Steam was injected into nine input wells arranged in an array of inverted five-spot patterns. In the completely confined center pattern, 14 temperature observation wells were installed to obtain thermal data and observe test progress. Late in the test, slugs of ammonia were injected to trace the flow paths of injected fluids. From the test area about 7,000 bbl of oil were produced. Data were obtained on areal and vertical temperature distribution, steam front advance, reservoir fluid movement and terminal saturations. This field test of a steam drive (I) demonstrated the feasibility of the method, (2) confirmed that the low residual oil saturations observed in the laboratory are obtained in the steam-swept region in the field and (3) provided recovery and conformance data for one set of field conditions. INTRODUCTION The Deerfield steam drive pilot test was conducted in a shallow sandstone containing 1,000-cp oil. The venture was undertaken cooperatively by the research and production departments of Carter Oil Co., which organizations have since been consolidated into Esso Production Research Co. and Humble Oil & Refining Co.. respectively. The production department was interested in steam injection at Deerfield because it appeared to be the most promising method of commercially producing this heavy oil deposit. The research department was interested in applying the new recovery method and in evaluating its performance in the field. At the time the test was begun, the initial oil saturation was not well known. Subsequent air coring and early pilot results confirmed that there was too little oil in place for profitable commercial exploitation by steam. Pilot termination at that time, however, would have been premature for evaluating field performance of the process, and the tert was continued to obtain additional data on steam injection as a recovery method. The test was located in Vernon County, Mo., about 10 miles north of the town of Deerfield and only a few miles from the Kansas border. The pilot site was selected as typical of the area. The location represented neither the highest nor the lowest oil saturation region in the acreage under lease in 1954. The steam drive was conducted in the Warner sandstone of Lower Pennsylvanian age. At the test site the top of the Warner occurs at about 160 ft subsurface and the formation is a fine- to medium-grained micaceous sandstone that dips gently to the northwest at the rate of 12 to 15 ft/ mile. A cross-section and permeability profile of the test location are shown in Fig. 1. At the pilot location the average total thickness of the Warner formation is about 43 ft, but the effective thickness for steam drive is 26 ft. Two distinct types of hydrocarbon saturation are apparent. The lower portion of the total sand, averaging about 17 ft thick, contains a very heavy asphaltic material that will not flow under the influence of a steam drive. This bottom interval, referred to as a dead oil residue, was not considered as part of the net sand undergoing steam exploitation. The initial formation and fluid properties of the upper 26 ft in the test area are summarized in Table 1, and variation of oil viscosity with temperature is shown in Fig. 2. Imbibition tests on preserved core samples taken at the end of the pilot test showed that the Warner sandstone was then neutral or slightly water-wet. Initially, the reservoir may have been strongly water-wet as indicated by low relative permeability to water during both water injection testing and early steam injection. PRIOR HISTORY Initial production tests of wells at the pilot site produced water with only a faint show of oil. No gas was produced except at Well 7-W in the pilot area and at another well about 1/3 mile northeast of the pilot. Prior to the start of the steam drive, a two-well water injection test and a two-well air injection test were conducted. No oil was produced by either. Water was pumped into Well I-W in the northeast corner of the pilot area with simultaneous production from Well 1 (Fig. 3). The air-injection tat was run at input Well 9-W and its offset, Well 2, in the southwest corner. Air and water injectivities were about the same when corrected for viscosity and pressure differences.

By Dwight L. Baker, Alexander Knoll

The work herein reported shows that galena in certain organic solutions of fatty acids becomes coated with lead soaps, and that this coating is not only highly water-repellent but is also repellent to certain organic liquids, particularly those of high surface tension; i.e., nitrobenzene, diphenylmethane. Wetting Properties of Galena in Nonaqueous Fatty Acid Solutions When a "captive bubble"I is withdrawn from a polished, plane galena surface under a nitrobenzene solution of stearic acid, the air bubble shows a decided tendency to "cling" to the mineral surface. The contact angle, therefore, was greater than zero, although it was not large enough to be measured quantitatively by the captive-bubble method." When pure nitrobenzene was substituted for the nitrobenzene-stearic acid solution, no clinging of the bubble was observed; viz., contact angle = zero. Although the contact angle developed in air-galena-nitrobenzene-fatty acid solution was small, the organic solvent repellency of the galena surface was great enough to enable good recovery in a laboratory flotation cell2 In Table I are given the results of flotation experiments using several different fatty acids dissolved in nitrobenzene.

Jan 1, 1943

By Alexander Knoll, Dwight L. Baker

The work herein reported shows that galena in certain organic solutions of fatty acids becomes coated with lead soaps, and that this coating is not only highly water-repellent but is also repellent to certain organic liquids, particularly those of high surface tension; i.e., nitrobenzene, diphenylmethane. Wetting Properties of Galena in Nonaqueous Fatty Acid Solutions When a "captive bubble"I is withdrawn from a polished, plane galena surface under a nitrobenzene solution of stearic acid, the air bubble shows a decided tendency to "cling" to the mineral surface. The contact angle, therefore, was greater than zero, although it was not large enough to be measured quantitatively by the captive-bubble method." When pure nitrobenzene was substituted for the nitrobenzene-stearic acid solution, no clinging of the bubble was observed; viz., contact angle = zero. Although the contact angle developed in air-galena-nitrobenzene-fatty acid solution was small, the organic solvent repellency of the galena surface was great enough to enable good recovery in a laboratory flotation cell2 In Table I are given the results of flotation experiments using several different fatty acids dissolved in nitrobenzene.

Jan 1, 1943

By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.' Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.' Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968

Albin, B. R. Billings, Mont. 28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S. 42 Broadway, New York, N. Y. 28 Barrett, C. P. 5338 Harper Ave., Chicago, 111. '28 Baum, Frank G., Cons. Hydro-Electric Engr Cassel, Shasta Co., Cal. '28 Bayless, William S. Russ Bldg., San Francisco, Cal. '28 Bean, Louis H.60 E. 42nd St., New York, N. Y. '28 Beatty, Roes J. 1105 First National Bank Bldg., Chicago, Ill. '28 Benwell, Oswald F. Hold Mags. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher, Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H. Iola, Kan. '28 Brown, Colvin B. Chamber of Commerce, Washington, D. C. '28 Bart, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1932

By J. R. Campbell

IN order to discuss the subject intelligently, it will be necessary to touch briefly on the forms in which sulphur is supposed to exist in coking coal to be carbonized in beehive or byproduct ovens. Sulphur is known to exist in coal as sulphides and sulphates, as can be determined experimentally. Then there is the so-called organic sulphur, i.e., sulphur in combination with the carbon, hydrogen, and oxygen of the coal, about which much has been written, but nothing definitely proven in an experimental way. In fact, so far as we know, there never has been developed a satisfactory and conclusive method in the laboratory for the direct determination of organic sulphur. For most coking coals, it can be safely assumed that the preponderance of sulphur is in the form of pyrite (FeS2). When exposed to comparatively low temperatures during the coking process, it loses its sulphur according to the following chemical reaction: 7FeS2 = Fe7S8 + 6S. It will be seen, therefore, that six out of the 14 atoms of sulphur (or 42.8 per cent.) are expelled, or volatilized. Fe7S8 remains in the coke as pyrrhotite, or magnetic sulphide of iron; this accounts for the highly magnetic properties of the powdered coke. A more commonly accepted reaction is FeS2 = FeS + S, in which the straight sulphide of iron is produced with 50 per cent. volatilization of sulphur. In the beehive methods of coke making, air is introduced in sufficient amounts to carry on the distilling and the coking processes, and the sulphur is oxidized along with the other volatile products: First, into sulphur dioxide (SO2), known by the pungent and suffocating odoremitted from the trunnel head; second, into sulphuric anhydride (SO3); and, finally, into sulphuric acid, as it comes into contact with the air and moisture. In a properly regulated draft on a beehive oven, there is never complete combustion of the gases. In other words, the coking process should be carried on in a reducing atmosphere, and a low-grade producer gas kept issuing from the trunnel head. For coals of about 30 per cent. volatile matter, the ratio of air to gas is 3 ½ to 1. In complete combustion, the ratio is 6 to 1, producing an extremely high temperature

Jan 1, 1916

H. A. BUEHLER, Rolla, Mo. -I consider the lead .and zinc deposits of the Mississippi Valley to be the result of descending waters. There are many features that we have not determined and yet when you see the general field relations, it seems to me that the cause and effect can be well explained by descending circulation. In the Joplin-Miami district, for instance, the ore deposits are connected with openings or with old cavity fillings which have a direct connection downward from the surface to practically 300 ft. In the Miami camp, in the western part of the field, some of the deepest orebodies are directly connected with water, channels; the same condition has been obvious and always present with the shallower ores. I speak of one deposit that I have examined more thoroughly than any other in that district, the Admiralty property, which contains large openings or caves at the deepest levels. It seems to me that waters which would pass upward through 1800 ft. of dolomite would be saturated with lime and magnesia so far as the carbon dioxide of those waters would dissolve them, and therefore, on

Jan 1, 1918

Carlisle: Jim Knapp, has been the good friend of hundreds-maybe thousands-of mining men in these western states in the last 40 or 50 years. Jim is going to talk about many of the mining camps of Nevada, where he has done plenty in the mining field during the last 50 years. Jim, for a starter, how did you happen to go to Nevada? Knapp: In the summer of 1902, two years after the discovery at Tonopah, the professor of mining at Stanford sent out myself and another student by the name of Joe Miller to make a report on the camp. We left San Francisco at 8 p.m., got to Reno the next morning, then took the train to Sodaville, arriving about 4:30 in the afternoon. The first man I met when I arrived at the Tonopah station was Tasker Oddie, a gentleman who later became the Govenor of the State and then a United States Senator. Before we got away from the stage station I also met S. H. Brady, the first mining engineer to put out his shingle in Tonopah. He afterwards became general manager of the West End Mining Co.

Jan 3, 1965

By R. W. Cahn, C. D. Graham

The rate of growth of a single grain growing into a strained aluminum single crystal, measured by the conventional heat-cool-etch technique, is shown to decrease with time at temperature. The growth rate measured by means of X-rays, with the sample continuously at temperature, is found to be linear. Evidence is presented to show that the decreasing growth rate obtained by the conventional technique is due to abnormal recovery in the strained grain, and that the recovery in turn results from the heating and cooling cycles, rather than from the effects of etching. The experimental apparatus is described in an appendix. FREQUENTLY, the rate of grain boundary motion during recrystallization is determined by heating a sample to a known temperature for a given time, cooling to room temperature, and etching to reveal the boundary position. The cycle of operations is repeated as many times as necessary to establish the rate of boundary motion. Although this heat-cool-etch technique has been used by a number of workers over a period of many years,'-!' other investigators have encountered difficulty with the method."'. " They have attributed the erratic results to the effects of repeated heating and cooling, or of etching, or both, and have adopted an alternative experimental procedure in which a number of identical samples are employed, each sample being cooled and etched only once. This alternative method ove1.comes some difficulties, but introduces others. In particular, the incubation periods of the observed grains are unknown: any effect of crystal orientation on growth rate cannot be determined easily. A preferable method would be to measure the motion of a recrystallizing grain boundary with the sample at temperature without etching," but such measurements have in the past been restricted to nonmetals. This paper describes the construction and operation of a device, the goniometer furnace, with which the position of a moving grain boundary between a recrystallizing grain and the strained single crystal into which it grows can be measured by means of X-rays, with the sample maintained continuously at temperature. Goniometer Furnace The operating principle of the goniometer furnace is shown in Fig. 1. The sample, in the form of a bicrystal strip, is surrounded by a furnace, not shown in the sketch, and can be rotated about the two axes A and B which intersect at the point where the X-ray beam strikes the strip. The strip is oriented so that one of the two grains gives a strong Bragg reflection, which is detected by a suitably placed Geiger-Miiller counter coupled to a counting-rate meter When the strip is moved parallel to its own length in the furnace, arrow C, so that the X-ray beam strikes the second grain, there is in general no strong reflection. By noting the position of the strip at which the drop in Geiger counter reading occurs, it is possible to determine the position of the boundary. Measuring the change in boundary position with time at temperature gives the rate of growth of the recrystallizing grain. Details of the construction and operation of the goniometer furnace are given in the Appendix. Measurements showed that the temperature in the furnace was uniform within ±10°C over its working length of about 28 cm. The temperature at the measuring position, i.e., at the point where the X-ray beam struck the sample, was estimated to be constant within ±2oC. Using the goniometer furnace, the position of a stationary boundary could be measured with a reproducibility of ±0.3 mm. At elevated temperatures, 500" to 625"C, with the boundary in motion and the X-ray reflection less sharp, the estimated accuracy of each measured boundary position dropped to about ±1 mm. Experimental Results The test pieces were single crystals of 99.6 pet A1 —principal impurities 0.19 pet Fe and 0.12 pet Si— 1 mm by 1 cm in cross section and 6 to 10 cm in length, grown by the strain-anneal method. This relatively low purity material was used because of the difficulty encountered in producing strain-anneal single crystals of very high purity—99.996 pet—

Jan 1, 1957

By A. Eilers

In a former paper on Western Smelting Works, I mentioned the great difficulty of obtaining accurate information in regard to the economy of the processes in practice; and to-day, although nearly two years have elapsed since my former paper was written, I am sorry to say that very little improvement has taken place in the keeping of accounts, and in the direction of a more systematic management in the majority of these works. But I am quite certain that by this time even the most sanguine furnace managers must have become convinced, from the experience of the last year, that somewhere in their processes there are enormous losses. Rates for the purchase of ores in 1873 were not as high as they were in former years in certain parts of the country ; labor was no 'higher than formerly; the demand for unparted lead was good throughout the year, with the only exception of the time of the panic, in the fall of 1873; yet there are, of between 40 and 50 works, not more than two or three in Utah and Nevada to-day, that have paid a reasonable interest on the capital invested.

By A. Filers

IN a former paper on Western Smelting Works, I mentioned the great difficulty of obtaining accurate information in regard to the economy of the processes in practice ; and to-day, although nearly two years have elapsed since my former paper was written, I am sorry to say that very little improvement has taken place in the keeping of accounts, and in the direction of a more systematic management in the majority of these works. But I am quite certain that by this time even the most sanguine furnace managers must have become convinced, from the experience of the last year, that somewhere in their processes there are enormous losses. Rates for the purchase of ores in 1873 were not as high as they were in former years in certain parts of the country ; labor was no higher than formerly ; the demand for unparted lead was good throughout the year, with the only exception of the time of the panic, in the fall of 1873; yet there are, of between 40 and 50 works, not more than two or three in Utah and Nevada to-day, that have paid a reasonable interest on the capital invested.

Jan 1, 1875

PERSONAL (Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during. the period May 10 to June 10, 1915: Robert M. Keeney, Somersville, Conn. C. A. Moffett, Birmingham, Ala. Emilio Mosonyi, San Salvador, C. A: A. W. G. Wilson, Ottawa, Canada. Junjiro Nagazumi, Fukuoka, Japan. G. H. Glover, Jr., Short Hills, N. J. Francis R. Pyne, Elizabeth, N. J. R. W. Brock, Vancouver, B. C. F. C. Alsdorf, Los Angeles, Cal. J. L. W. Birkinbine, Philadelphia, Pa. W. J. Loring, London, England. Roy H. Allen, Jamesburg, N. J. R. A. Bull, Granite City; 111. Francis Andrew Thomson received the degree of Master of Science from the Colorado School of Mines at the recent commencement exercises. The subject of his thesis was Stamp Milling and Cyaniding.

Jan 7, 1915

By R. L. Bleifuss

The object of this study was to evaluate the oxidized taconites of the western Mesabi iron range and to establish a correlation between the various basic taconite types and their concentratability. The initial work included a study of the original mineralogical and stratigraphic facies of the fresh taconite and traced the oxidation and leaching patterns developed during the conversion of this material to oxidized taconite. Subsequent studies have extended this work to include the semitaconites and also the wash and heavy media ore types widely developed in the area. Each basic original mineralogical facies or taconite type produces during alteration an equivalent secondary oxidized facies which has a unique mineralogical composition and texture. These control the concentratability of the oxidized taconites. Actually the influence of the original mineralogical composition of the iron formation extends even further and determines whether the most likely product of oxidation and leaching will be a wash ore or a heavy media ore and even to the direct shipping ores where the ratio of hematite to goethite is largely determined by the original taconite type. The relationship between original taconite, oxidized taconite, semitaconites, and wash and heavy media ores is briefly summarized in Table I. The terms are not precise and in some instances tend to overlap. The table is intended to point out only the essential differences between the various materials. The original taconite was dominantly composed of mixtures of magnetite, iron carbonate, iron silicate, and quartz (chert). In a few thin stratigraphic units, hematite was present as an original constituent. The alteration of the original taconite to oxidized taconite has resulted from the circulation of ground waters through an initial fracture system related to minor structures in the iron formation. The chemical reactions have involved the oxidation and decomposition of original minerals such as magnetite, iron carbonate, and iron silicates to hematite or goethite. The alteration at this early stage is characterized by pseudomorphic replacement of the original minerals by oxidation products although retaining the major textural features of the original taconite. There was very little secondary migration of iron at this stage and the total iron content of the rock has been only slightly increased. Further alteration of this material to form a semi-taconite, a wash or a heavy media ore, involves extensive removal of silica in solution and significant redistribution of iron units. Wash and heavy media ores are developed by the growth of coarse secondary iron layers, dominantly goethite, coupled with the removal of silica in solution and decomposition of the cherty layers. This paper is concerned primarily with the materials classified as oxidized taconites which are characterized by oxidation of the original mineral constituents with little secondary enrichment. The area studied, shown on the index map, Fig. 1, extends some 30 miles along the strike of the Biwabik formation roughly from Hibbing to Coleraine. This study was greatly facilitated by the basic stratigraphic and mineralogical studies of Gruner1 and white2. The bulk of the material in this presentation represents a portion of the author's contribution to a study sponsored by the Great Northern Railway on the oxidized taconites of the western Mesabi.3 METHOD OF APPROACH A total of 106 drill holes, representing some 30,000 ft of drilling, were examined and sampled. The drill holes were logged and some 1500 composite samples were prepared for chemical analysis and bench scale metallurgical tests. These samples were analyzed for total iron and ferrous iron; and magnetite iron was determined by a standard Davis tube test at minus 200 mesh. Standard reduction roast tests using 150-gram samples of minus 10 mesh material were made on these 1500 composite samples with a mixture of H2, CO2, N2, and H2O at a temperature of 650°C. This roasted material was pulverized through 150 mesh and concentrated in the Davis tube. The iron recoveries and concentrate grades obtained on the roasted products were used to assess the concentratability of the oxidized taconites. Detailed mineralogical work was done on thin sec-

Jan 1, 1964

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By Charles A. Schffer

Several months ago, some specimens of the minerals occurring at the Etta tin mine, Dakota, were received at the laboratory of the Cornell University. On examining the heavy brownish-black portion, which I presumed was the tin-stone, I was surprised to find only a faint indication of tin. Further investigation showed the mineral to be tantalite. On searching carefully all the fragments received, a considerable quantity of that mineral was found, and only a single streak of cassiterite, which was attached to a mass of spodumene. Another lot of specimens, from the same locality, consisted of

Jan 1, 1885

By F. A. Emmerton

I have used for about two years, in the laboratory of the Joliet Steel Company, a rapid method for the determination of phosphorus in iron, steel, and ores, which possesses one or two features sufficiently novel to warrant description. In general, it is the method described by Mr. Benjamin B. Wright (Transactions, vol. x., p. 197), involving the precipitation of the phosphorus by means of molybdate solution, and its estimation in the yellow precipitate by reduction of the molybdic acid, and titration of the resulting oxide with a standardized permanganate solution, according to the principles laid down by Werncke (Fres, Zeit., vol. xiv., p. 1). In the use of this method, I had difficulty at first in obtaining a yellow precipitate of reasonably uniform composition. It is a well-known fact that, to secure this result, the conditions of precipitation must not vary. The principal condition is temperature; and acidity, concentration, proportion of nitrates and chlorides, and time, are important elements. I am aware that uniformity in these conditions has been obtained to a reasonable extent by many chemists,. so that they are enabled to use with success, methods based on the

Jan 1, 1887

By P. L. De Bruyn

The adsorption density of dodecylammonium ions at the quartz-solution interface has been Theadsorptiondensitydetermined as a function of collector concentration and pH. A ten thoushasbeenandfold range of amine salt concentration was covered at neutral pH. Experimental results show that over a thousandfold concentration range at neutral pH, the adsorption density (I) is proportional to the square root of collector concentration. Except at high concentrations, I increases with increases with increasing pH, but in general this effect is surprisingly small. . , . . A critical pH curve has been established for the flotation of quartz with dodecylammonium acetate. The conditions along the flotation curve are correlated with the adsorption measurements. THE behavior of collectors at the mineral-solution interfaces is usually explained in terms of an ionic adsorption process. Through the distribution of collector ions between the solid surface and the- co-existing solution phase the mineral is believed to acquire a water-repellent surface coating. Quantitative adsorption studies have been made on simple flotation systems1-4 only within the last few years. Such investigations were made possible by the adoption of the radiotracer method of analysis. As a consequence of these studies a new parameter has been added to aid the understanding of the flotation process. The research investigation to be discussed in this paper was undertaken to obtain a better understanding of the behavior of a cationic-type collector. This objective was approached through the determination of the distribution of dodecylammonium acetate between the quartz-solution interface and the solution as a function of the collector salt concentration and pH. To bring this investigation to focus on the more practical aspect of flotation research, an attempt was also made to correlate the adsorption results with actual flotation tests. Quartz: A —100 mesh ground crystalline quartz was infrasized; the products of the third and fourth cones were mixed together and reserved for experimental purposes. This stock material was cleaned by leaching in boiling concentrated HC1. After leaching the quartz was rinsed with distilled water until the filtrate showed no trace of chloride ian. It was then washed several times and dried. The qwrtz had a specific surface of 1400 cma per g as deterhined by the krypton gas adsorption method. Collector: The distribution of dodecylammonium acetate between the quartz surface and the solution phase was determined by the radiotracer method of analysis with carbon 14 as the tracer element. The radioactive amine salt with C" synthesized into the hydrocarbon chain5 was supplied by Armour and Co. The tracer element was located adjacent to the polar group. The radioactive salt as received had a specific activity of about 0.14 mc per g. When desired, dilution of this activity was effected by addition of non-radioactive dodecylammonium acetate also supplied by Armour and Co. ........ All other inorganic reagents used in this research were of reagent grade. Conductivity water was used for making up all solutions. Adsorption Tests: Two different experimental methods were used. In the first, to be designated as the agitation method, a weighed amount of quartz and a measured volume of amine salt solution were agitated in a 100-ml or 50-ml glass-stoppered pyrex graduated cylinder. The cylinder was filled with solution up to the stopper, since erratic results were obtained when an air space was left over the suspension. Time of agitation varied from 1 to 2 hr. Preliminary tests at different agitation times showed that the amount adsorbed remained constant for all agitation times exceeding 1/2 hr. After this conditioning period, the solids were separated from the solution by filtration through a Buechner fritted-disk funnel. The solution was re-circulated 10 times or more to allow the fused silica disk to come to equilibrium with it. Determinations of the amount of amine adsorbed on the frit itself indicated that this amount was less than 10 pct by weight of the amine acetate abstracted by 10 g of quartz. The funnel with quartz covered by a thin layer of solution was then centrifuged for approximately 5 min, at which time the moisture content of the solids was reduced to about 5 pct by weight. The wet quartz was blown into a tared beaker, re-weighed and allowed to dry at room temperature. A final weighing was then made to determine the moisture content. The second experimental method, similar to the procedure adopted by Gaudinand Bloecher,' will be referred to as the column method. Two liters of solution were passed through a bed of quartz contained in a Buechner funnel attached to a pyrex separatory funnel by means of a ball and socket joint. Preliminary tests showed that increasing the volume of solution above 2 liters does not give a measurable increase in adsorption. From 4 to 4 1/2 hr were required for 2 liters of solution to pass through the column. The moisture content of the quartz was again reduced to a minimum by centrifuging. A slightly modified column apparatus was used for experimenting with alkaline amine solutions. The same basic unit was used, but the underflow from the Buechner funnel was again fed into a Separafory

Jan 1, 1956

MINING METHODS. JAY A. CARPENTER, Chairman P. B. BUCKY, Vice-Chairman CLYDE E. WEED, Vice-Chairman ROY A. HARDY, Secretary Alluvial Mining CLINTON BERNARD O. B. PERRY NORMAN CLEAVELAND C. M. ROMANOWITZ R. B. EARL! NO J. B. STAPLER BENERE H. GRANT CHARLES THURMAN Open-Cut Mining Iron A. D. CHISHOLM P. G. HARRISON G. E. DIEHL EARL E. RUNNER G. E. LEVEQOE

Jan 1, 1942

By R. W. Raymond

In connection with the paper of Mr. Locke on Gilsonite or Uintahite (Trans., xvi., 162) read at the Salt Lake session of the Utah and Montana meeting, in July, 1887, the following data may be of interest and value. In December, 1887, I received from Mr. William Wagner, Seeretary of the Denver & Rio Grande Railway Co., a box of specimens of an asphaltic mineral from Utah. In the course of the correspondence which followed, I learned that the box had been forwarded by Mr. J. A. McMurtrie, of the firm of McMurtrie & Streeter, railroad contractors, Denver, Col. Mr. McMurtrie was, in 1883, chief engineer of the Denver $ Rio Grande Railway, and the mineral mas first brought to his attention in that year by Mr. Thomas H. Wigglesworth, who was then employed in making preliminary reconnaissances for wagon-roads to be used in constructing the Utah extension (now the Denver, Rio Grande $ Western) of the railway. Mr. Wigglesworth, I understand, was subsequently chief engineer of the Colorado & Utah Midland, and is now again employed by the Rio Grande. He writes substantially as follows concerning this mineral:

Jan 1, 1889