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

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By M. T. Martinson, I. W. Nicholson, C. J. Chindgren, F. P. Williams, L. C. Bauerle, S. F. Ravitz

THE vanadiferous shales of southeastern Idaho and southwestern Wyoming constitute the largest known reserve of vanadium in the United States.1 These deposits have never been exploited except for the relatively small amounts of vanadium recovered by the Anaconda Copper Mining Co. in the treatment of phosphate rock from southeastern Idaho. The major domestic source of vanadium has been the sandstone ores of southeastern Utah and southwestern Colorado. Early in World War II, it appeared that these ores could not meet the greatly increased demand for vanadium, so the investigation described in this report was undertaken to develop processes for the recovery of vanadium from the Idaho-Wyoming deposits. The utilization of these deposits became unnecessary, however, because of greatly expanded production from the Utah-Colorado sandstone ores and the continued availability of vanadium from other sources, chiefly Peru. The major use of vanadium is as an alloying agent in the manufacture of high-quality steels. Vanadium constructional steels usually contain 0.05 to 0.20 pct vanadium, which refines the grain and increases the strength, elastic limit, and resistance to shock and fatigue. Vanadium tool steels not used in high-speed work contain 0.10 to 0.60 pct whereas high-speed tool steels contain 1.0 to 4.0 pct. Vanadium compounds are used as catalysts (principally for the oxidation of SO2 to sulphuric acid and of naphthalene to phthalic acid) and in the paint, chemical, ceramic, dye, and printing industries. The selection of the particular ore deposit to be exploited would involve consideration of many factors besides the metallurgical results that might be obtained. Chief among these would be the reserves of ore available, the grade of the ore, and the mining costs. As very little was known about any of these factors, it was necessary to investigate methods of treatment of all the ores under consideration, working with samples obtained in the course of the exploration work, even though they were not positively representative of the whole deposit from which they were taken. Because of wartime conditions prevailing when this investigation was started, first consideration was given to processes that could be put into operation most quickly and would involve minimum use of strategic materials, even though these processes might not be the most economical.

Jan 1, 1947

By Walter Kauzman

ALL viscous or plastic flow of incompressible matter is the result of shear strain; the changing shape of any body that is being plastically deformed can be completely described in terms of the shear strain occurring at each point in the body.[t] Furthermore, the relative amounts of shear strain occurring in different parts of a body under stress depend upon the relative rates of shear strain at those different points, so that if the dependence of the shear rate of any material on the temperature, shear stress, previous history, etc., were understood, the principles of plastic deformation would be known, and we could calculate how a body made of a given material, having a given shape, and subject to a specified system of forces, would change its shape with time. It may be said, then, that the problem of plasticity resolves itself into, first, the problem of the rates of pure shear processes, and second, the application of what is known about pure shear to actual cases. It is the purpose of this work to investigate the former problem -i.e., the dependence of shear rates on temperature, stress, etc.-from the standpoint of recent developments in the field of chemical-rate theory and with particular reference to the phenomena occurring in the creep of metals and in the plastic flow of crystalline solids in general. It is left for the mechanical engineer, and perhaps the expert in hydrodynamics, to deal with the problem of applications.1 RESOLUTION OF MACROSCOPIC SHEAR INTO MICROSCOPIC MOVEMENTS; RESEMBLANCE TO CHEMICAL REACTIONS Just as any large body is made up of many small units, or atoms, so macroscopically observable shear is the result of many microscopic unit shear processes; just as the understanding of the behavior of large bodies demands the understanding of the atoms of which it is made, so the understanding of macroscopic shear demands the understanding of these fundamental unit processes. The study of shear from this "atomistic" point of view has made considerable progress. There has been fairly complete understanding of shear processes in gases for a long time, at least for nonturbulent flow, as a chapter on gaseous viscosity in any text on the kinetic theory of gases will prove. In recent years Andrade2 and Eyring3 have presented important theories for the flow of liquids and amorphous solids. Becker,4 Orowan,5 Taylor,6 Burgers,7 and Kanter8 have considered the

Jan 1, 1941

By Porter W. Shimer

The solution used in the following method for phosphorns-determination is the filtrate obtained in the nitric and sulphuric acid method for the determination of silicon (Transactions, vii., 346). This filtrate, being easily and quickly obtained, and always quite free from silica, is a desirable one for phosphorus-precipitation. IN order, however, to get all the phosphorus in a precipitable form the solution must be made under conditions more strongly oxidizing than simple solution in boiling nitric acid. In a solution thus

Jan 1, 1889

By W. O. Philbrook, K. M. Goldman, G. Derge

EQUILIBRIUM conditions for steelmaking reactions have been studied extensively over the past two decades by a .number of investigators, with gratifying results. Equilibrium data are essential to the understanding of any process, and such knowledge has the practical utility of placing a limit beyond which control measures cannot succeed. When, however, the driving rate of an industrial process is so fast that there is not time for reactions to reach equilibrium, it then becomes necessary that the factors which control the rates of reaction be known in order to establish full control of the process. The desulphurization of molten pig iron by slags within the iron blast furnace is one such process in which the actual degree of sulphur absorption by the slag does not approach the equilibrium distribution obtained for similar slag-metal systems in the laboratory.' A study of the rate-controlling factors governing the desulphurization of iron by slags is becoming increasingly important as the sulphur content of raw materials increases with depletion of higher grade ores and coal. Following up an initial study on kinetics,' this paper reports some results of a continuing laboratory investigation on the mechanism of sulphur transfer between molten iron saturated with carbon and slags of the CaO-SiO,-A12O3 system. Laboratory experiments cannot reproduce in detail the conditions which prevail in the hearth of a blast furnace, but they will contribute to an understanding of the smelting reactions and perhaps will explain some apparent inconsistencies in the factors controlling the equilibrium distribution of sulphur between iron and slags under reducing compared with oxidizing conditions. The mechanism of a reaction—that is, the individual steps and the sequence in which they occur to produce the overall reaction which is ordinarily observed—must be elucidated to learn which steps are the slow ones, or "bottlenecks," that fix the pace of the process as a whole. In the desulphurization reaction, for example, the overall rate might, in principle, depend upon the rate of diffusion of sulphur in the metal or in the slag, upon the speed of some homogeneous reaction taking place entirely within one of the phases, or upon some heterogeneous reaction taking place across the slag-metal interface. Even some side reaction or the back reaction might have some influence. Evidence on all of these points will be presented in this paper. The rate of diffusion of sulphur in both iron and slag is so slow that it seems necessary to assume that convection provides the mechanism of carrying

Jan 1, 1951

By O. C. Wheeler

The reports for the years 1942 and 1943 were written in 1943 and 1944, respectively, and were summarized at the meetings of the Institute in February of those two years, but the manuscripts were held until released for publication in 1945. 1942 Lack of transportation facilities during 1942 resulted in a sharp curtailment of producing operations in Colombia at the middle of the year, and production of crude for export was thus greatly affected. Total production in 1942 amounted to only 10,617,008 bbl. Of this amount the Tropical Oil Co. produced 9,453,995 bbl., which includes 126,607 bbl. of petroleum condensate, and the Colombian Petroleum Co. produced 1,163,013 bbl, from its Barco property. The following summary, showing a comparison of the number of barrels of crude produced during the years 1941 . and 1942, reflects the extent to which producing operations were reduced during 1942: These above figures do not include any production recovered from Condor's (Shell's) Casabe wells during testing operations. An active exploratory drilling Program was carried out by several of the major companies, and the year 1942 established a record for wildcatting activity in Colombia. Excluding development operations on the Shell's Casabe wells on the Yondo concession, 13 wildcats were completed. Eight of these were in the Magdalena Valley, and all were abandoned; five were on the Barco Concession, and of these four were completed as producers. Particularly notable among the petroleum developments during 1942 was the continued success of drilling operations on the Shell's Yondo Concession of Compania Colombiana de Petroleos El Condor opposite Barranca-Bermeja. In 1941 the discovery well, Casabe No. I, was drilled and completed with an estimated initial production of approximately 480 bbl. of 19 1/2 A.P.I. gr. oil per day. In 1942, seven stepouts from the discovery well were successfully completed with initial production ratings ranging from 150 to 1230 bbl. per day. An extensive wildcat program on the Barco Concession of the Colombian Petroleum Co. yielded favorable results with the completion of four producers in the Socuavo and Tres Bocas areas; a fifth test, Sardinata Norte No. I, was abandoned at 500;" feet. Wildcatting operations in the lower Magdalena Valley area were initiated in 1942 With the drilling of a deep test, El Dote No. I, by Compania de petroleo Shell de Colombia. The well was a failure and was abandoned at a depth of 10,046 (?) feet. Wildcats on which drilling operations were being conducted at the end of the

Jan 1, 1945

By Oscar Lee

RESERVE Mining Co., owned jointly, by Armco Steel Corp. and Republic Steel Corp., controls 9% miles of magnetic taconite ore on the eastern end of the Mesabi Range lying between Mesaba and Birch Lake. The ore reserve which can be mined by open pit methods is conservatively estimated at 1.5 billion tons under a shallow, loose overburden requiring no rock stripping. Taconite now being mined is in the upper cherty horizon. It has been metamorphosed by the intrusion of gabbro and most of the iron oxide is altered to magnetite. The nonmagnetic portion of the iron is practically all in the form of silicate. The magnetic iron is finely disseminated through the rock and requires grinding -150 mesh for clean liberation of the iron oxide from the gangue.

Jan 5, 1954

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufliciently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion .4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. "I hey believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They (lid not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (1) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led hint to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed (luring the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (AS208)

Jan 1, 1942

By G. R. Countryman, G. H. Thomas, I. Fatt

Miscible displacement in both thewetting and non-wetting phase has been studied in two-phase systems. Experimental data show that dispersion is a function of saturation and cannot be predicted from dispersion theory developed for single-phase miscible displacement. Some of the effect of saturation on dispersion is a result of the development of dead-end pores or a dendritic pore structure in multiphase systems. The presence of dead-end pores or dendritic structure is confirmed by pressure transient studies. INTRODUCTION Displacement by flooding with a miscible liquid is a possible means for recovering the estimated two-thirds of the oil that remains behind after primary production. The immense economic importance of a process that can recover such large quantities of oil has led to extensive laboratory studies of miscible displacement. As usual in production research, most laboratory studies of miscible displacement have not attemped to reproduce all of the conditions existing in a petroleum reservoir. In the early stages of investigation the need has been for information on the broad, basic principles of the phenomena involved in miscible displacement. The effects of overburden pressure, reservoir temperature, and wettability have been considered of secondary importance. However, one property of a petroleum reservoir which is expected to be of major importance and yet has been omitted from many laboratory studies is the presence of interstitial water. Two possible effects of interstitial water on the displacement mechanism in the hydrocarbon phase immediately come to mind. First, from the general1y accepted theory that capillarity governs the distribution of oil and water in porous rock one would expect that for water-wet rock the water will be in the small pores and oil in the large pores. A miscible displacement of oil carried out in the presence of water is operating in a pore size distribution shown in Fig. lb, whereas if the same test had been performed with only one phase present the pore size distribution is as shown in Fig. la. Although there is not yet a theory of miscible displacement which explains in detail the effect of pore size distribution, one would expect the differences between Figs. la and lb to influence the displacement efficiency. A second factor which may make a multiphase system different from a single-phase system is the presence in the multiphase system of dead-end pores or dendritic structure. Experiments of various kinds on reservoir rock have led to the belief that all pores in the network structure of a porous rock take part in conducting fluid during single phase fluid flow.1,2 There are then no dead-end pores and no fingers or dendritic structures containing stagnant fluid. In a multiphase system, however, the second phase may

By R. M. Brown, W. J. Murphy, B. M. Kapadia

An investigatiott was conducted to study the influence of nitrogen, titanium, and zirconium on the boron llardenabilzty effect in a low-carbon constructiona2 alloy steel. The experimental steels investigated exhibited a significant variation in hardenability, the variation being dependent on the interactions of boron, titanium, and zirconium with the nitrogen. Only the boron not combined with nitrogen was effective in increasing hardenability. Titanium, and with lesser effectiveness zirconium, combined with available nitrogen, thereby protecting the boron. The hardenabil-ity effect mas related to an empirical expression for the "effective" boron content, P, deduced from experimental evidence of these interactions. The hardenabzlity effect reached a maximum at about 0.001 wt pct 0, and decreased somewhat as P increased further. The physical understanding of this relationship is discussed. FOR many years boron has been added to steels to obtain high hardenability. Although a great deal of research has been conducted on boron-treated steels, certain aspects of the boron hardenability effect have not been fully understood. For instance, the magnitude of the hardenability effect has been observed to vary markedly, depending on the steelmaking technique, even when the amount of boron in the steel was essentially constant. Furthermore, the optimum amount of this element to be added has not been definitely established. A better understanding of the boron hardenability effect is essential because too small an addition of boron is likely to be ineffective, while an excessive amount can cause brittleness'' and hot shortness. The findings of earlier investigations have shown that the hardenability effect cannot be consistently related to the amount of boron added or retained in the steel. Grossmann observed that in a 0.60 pct C steel the hardenability increased to a maximum with mold additions up to about 0.0025 pct B and then decreased with larger additions. Other investigators5 likewise reported a maximum in the hardenability at about 0.003 pct B. Crafts and Lamont, however, found that in commercial open-hearth heats of medium-carbon steel the hardenability increased linearly with boron up to 0.001 pct and remained essentially unchanged with larger percentages up to 0.006 pct. Other investigators7,' also observed a rather constant hardenability effect in the range about 0.0005 to 0.0035 pct B. These observations and other evidence suggest that the effectiveness of boron in increasing hardenability probably depends, in addition to the amount, on the form of boron retained in the steel, this form being influenced by the presence of other elements. Both oxygen and nitrogen apparently exert the strongest influence on the hardenability behavior, since, at the temperature of liquid steel, boron readily combines with these elements, thereby losing its effectiveness as most experimental evidence seems to indicate. For consistent recovery of the boron effective in increasing hardenability, it is necessary that the oxygen and nitrogen in the steel be either reduced to extremely small amounts by the steelmaking practice or neutralized by combination with other elements before the addition of boron. The importance of achieving adequate deoxidation prior to the addition of boron in order to realize the full hardenability effect of boron has been sufficiently emphasized by earlier investigators. Digges and Reinhart' and others have investigated the role of nitrogen and have shown that nitrogen also interacts with boron and reduces or nullifies altogether its effect on hardenability. Moreover, their work also demonstrated that the addition of strong nitride formers such as titanium and zirconium reduce the deleterious effect of nitrogen on boron hardenability by combining with nitrogen to form stable nitrides. Another element which has a pronounced influence on the boron hardenability effect is carbon. It has been shown7'10 that the hardenability effect of boron diminishes with increasing carbon content, and becomes almost negligible at the eutectoid composition. This observation is useful in comparing the potential increase in hardenability from boron of steels with different carbon contents, but is not relevant to a study of the effects of normal steelmaking variables. The amounts of oxygen and nitrogen in steel vary with the steel composition and steelmaking practice employed. Most commercia1 low-alloy steels are fully deoxidized by the addition of silicon and aluminum, or other strong deoxidizers, which adequately protect the boron from oxidation. In addition, one or more of the elements such as titanium or zirconium are usually added, either separately or in combination with boron, in the form of complex ferroalloys, to protect boron from combination with nitrogen in the steel. However, the actual amount and type of addition employed for a given processing requirement are usually selected by trial and error, and have a rather limited range of applicability. As a result, substantial variations in the hardenability of boron-treated steels are often observed in practice, particularly when the nitrogen content of the steel is a significant processing variable. These variations might therefore be reasonably attributed to the interactions between boron, nitrogen, and titanium or zirconium present in the

Jan 1, 1969

By H. I. Smith

CONTENTS [PAGE Problems of Mining and Processing Mineral Aggregates (TP 1649, by NATHAN C. ROCKWOOD, Min. Tech., Nov. 1943. Discussion by H. I. SMITH, IRVING WARNER and the author) t Mica in War (TP 1749, by RUSSELL G. WAYLAND, Min. Tech., July 1944. Discussion by H. S. SPENCE) 3 Three Roofing-granule Plants in Pennsylvania (TP 1787, by RICHARD M. FOOSE, Min. Tech., Jan. 1945. Discussion by H. I. SMITH)5 Methods of Prospecting and Mining Optical Calcite in Montana (TP 1896, by E. W. NEWMAN, Min. Tech., Nov. 1945. Discussion by W. C. STOLL and FRANK C. ARMSTRONG, and the Glass Sand and a Glass Industry in Puerto Rico (TP 1939, by HOWARD A. MEYERHOFF and J. EARL FRAZIER, Min. Tech., Nov. 1945. Discussion by A. M. SHORT, the author and PHILIP The "Bonanza" Mica Operation of Purdy Mica Mines, Limited, Mattawsn Township, Ontario (TP 2154, by HUGH S. SPENCE, Min. Tech., March 1947. Author's supplement and discussion by JOHN A. BAKER, E. J. LINTNER, and the author) 7 Process for Manufacture of Dead-burned Magnesite and Precipitated Calcium Carbonate from Dolomite (TP 2155, by ROBERT D. PIKE, Min. Tech., March 1947. Discussion by 0. C. RALSTON and the author) 9] Problems of Mining and Processing Mineral Aggregates H. I. SMITH*-Mr. Rockwood has presented a very interesting paper on problems of the mineral aggregate industry in meeting specification requirements, which apparently are ever decreasing in tolerance. May I call attention to a method of mineral separation that may be of value in separating the flat aggregate particles from the more angular ones and possibly the soft particles from the hard. The method is the old Pardee spiral coal separator, extensively used many years ago in the anthracite region for separating rock and bone from anthracite coal.1 The success of the process depends on the relative coefficient of friction of the aggregate particles to be separated rather than on their relative specific gravity. The flat and the soft particles normally will slide more slowly and stay on the inner spiral until they reach the delivery spout at the bottom whereas the round and the angular pieces will work to the outer edge and fall off into a spiral of larger diameter. The capacity of the separator is increased materially by having three inner spirals, with a separate feed for each, on which the particles travel more slowly, and one outer spiral from which the more rapidly traveling pieces slide to the bottom. IRVING WARNER*-I have long been convinced that much of the equipment and methods developed for mineral dressing might be advantageously employed in the mineral aggregates industry, and more particularly in the production of sand and gravel. The two industries are not well acquainted with each other or their problems. They have separate trade publications. The difficulty with the situation is that there are few large sand and gravel plants and few provided with technical services in their own organization or by retainer. This does not refer to engineering organizations but rather to improvement of plant technic in processing.

Jan 1, 1947

By H. O. Hofman

The substance of this paper was prepared for the Seventh International Congress of Applied Chemistry, held in London, May, 1909, under the title, Some Developments in Blast-Roasting. In the absence of the author, a short abstract of the paper was read, and the abstract only will appear in the proceedings of the congress. The present paper has been partly rewritten and considerably enlarged by information gained since the original was prepared; also some illustrations have been added. Blast-roasting* is a generic term for the process of forcing air through finely-divided metallic sulphide with the object of roasting and agglomerating in a single operation. At first the process was confined to a galena-concentrate; lime, limestone, or gypsum was added, to serve both as a diluent to keep separate the particles of galena that they might be thoroughly oxidized, and as a flux that the partly-roasted ore niight be agglomerated by the formation of some slag. Later it was extended to treat other metallic sulphides. The leading processes were the Huntington-Heberlein and the Savelsberg of Europe, and the Carmichael-Bradford of Australia. In the United States and Canada, the Huntington-Heberlein process has found application in some instances with galena-concentrates, for which it was originally intended; but this class of ore is not often treated alone, hence the process has had to be modified to suit conditions. The Savelsberg process has been transplanted to this country in about its original form. The Carmichael-Bradford is not used at present. The changes called for in the Huntington-Heberlein process to adapt it to the class of lead-bearing ores usually smelted have been the

Jan 1, 1911

By R. W. Heckel, R. E. Trabocco

The recovery process in 400 Monel filings was followed, principally, by using the Warren-Averbach technique of X-ray peak profile analysis. The deformation fault probability, a, was 0.006 in samples of unannealed filings. a , the twin fault Probability , was approximately 0.002 in samples of unannealed filings. Both a and 0 were found to "anneal out" at 600°F. The effective particle size and mzs strain increased and decreased in the (111) direction, respectively, with increasing annealing temperature. The actual particle size was found to be almost equivalent to the effective particle size. Tile small values of deformation and twin fault probabilities accounted for the similarity in values of the effective and actual particle sizes. Stored strain energy and dislocation density calculations based on rms strain decreased with increasing annealing temperature. The dislocation density decreased from 10" per sq cm in the unannealed filings to 10' per sq cm in the partially re-crystallized filings. The square root of the dislocation density based on strain to that based on particle size indicated a random dislocation distribution in the unannealed filings. The dislocation arrangement changed to one with dislocations in cell walls with increasing annealing temperature. THE recovery processes which occur in metals are generally thought to be a redistribution and/or annihilation of defects.' Investigators' have shown that recovery processes can be characterized by X-ray line-broadening analyses. Michell and Haig4 measured the stored energy of nickel powder by calori-metry and found the value to be greater by a factor of 2.5 than that from X-ray data obtained by the Warren-Averbach technique.= Minor increases in particle size occurred up to 752°F (recovery), while above 752°F the particle size increased greatly due to recrystalliza-tion. X-ray microstrain values decreased between room temperature and 392"F, remained constant from 392" to 752"F, and decreased from 752°F to a negligible value at 1112°F. Faulkner developed an equation for calculating stored strain energy based on X-ray line-broadening data which gave a closer correlation of measured and calculated stored strain energy based on the data of Michell and Haig. The stored strain energy released during recovery is predominately dependent on the decrease in dislocation density which was p-enerated from cold work.7 Stored energy has been measured8 in alkali halides during recovery and recrystallization and 80 pct of the stored energy was found to be released during recovery. Dislocation distributions have been studiedg in a number of fcc metals by thin-film electron microscopy. Howie and Swann" found the stacking fault energy of copper and nickel to be 40 and 150 ergs per sq cm, respectively. ~rown" has pointed out that these stacking fault energy values should be corrected to 92 and 345 ergs per sq cm, respectively. The dislocation distribution of a metal is directly dependent on the stacking fault energy of the system. Metals of high stacking fault energy such as aluminum cross-slip readily and do not form planar arrays of dislocations. Metals of lower stacking fault energy such as stainless steels" do not cross-slip readily. Cold-worked nickel has been found to form a cellular dislocation structure after annealing.13 The relatively high stacking fault energy of nickel and copperlo to a lesser extent favor cellular structures of dislocations rather than planar arrays after deformation. The present study of recovery was carried out on a Ni-Cu alloy (Monel 400) to compare with prior studies for pure nickel and pure copper. X-ray line-broadening techniques were used to measure the effect of recovery temperature on rms strain and particle size and the results were compared with previous studies on copper'4-'7 and nickel., Calculations were also made on stacking fault probabilities, dislocation density, dislocation distribution, and stored strain energy as affected by temperature. EXPERIMENTAL PROCEDURE The nominal analysis of the Monel 400 used in this investigation was: 66.0 pct Ni, 31.5 pct Cu, 0.12 pct C, 0.90 pct Mn, 1.35 pct Fe, 0.005 pct S, 0.15 pct Si. The annealed material was cold-reduced in two batches, one 50 pct and the other 80 pct. It was originally planned to conduct line-broadening studies of these bulk samples; however, rolling textures that developed produced low-intensity peaks which were not suitable for line-broadening analysis. Filings were prepared at room temperature from both the 50 and 80 pct cold-reduced specimens, series A and series B, respectively, and were not screened prior to heat treatment or X-ray studies. Heating to the annealing temperature, 200" to 120O°F, was accomplished in a matter of minutes in a hydrogen atmosphere. Following heat treatment, some of the filings were mounted and polished for microhardness measurements with a Bergsman microhardness tester, using a 10-g load. A G.E. XRD-5 diffractometer using nickel-filtered Cum radiation was used to obtain all diffraction patterns. Only (111)- (222) line-broadenin data were used in the present study since the {400f peaks were too weak to use. The Fourier analysis of the (111) and (222) peak

Jan 1, 1969

By Howard I. Smith

POTASH is of prime importance as a plant food and is also widely used in industry. The term "potash was applied to a crude pearlash obtained by evaporating, in iron pots, solutions leached from plant ashes. Later it included caustic potash obtained by treating pot ashes with lime, and now it is applied generally to various compounds of potassium used by agriculture and industry. Herein it applies to the theoretical equivalent in potassium oxide (K20)--a compound never found in nature or manufactured in commerce but generally used as a common denominator for comparison of all potassium compounds. Potash was made from plant ashes at an early date, but potassium in mineral form was not noted until 1797, when it was identified in leucite.3 The importance to plant life of potash in the soil was first recognized by von Liebig3 and his published reference thereto appeared in 1840. In 1843, potash was discovered in the brine of a well drilled for salt near Stassfurt. HISTORY OF THE AMERICAN POTASH INDUSTRY Among the colonists reaching Virginia in 1608 were men from Poland skilled in making potash from wood ashes19 and records show that the production of potash was begun in other colonies also, soon after their establishment. The American product entered the trade in 1635, and at various times since that date the production of potash for industry has been subsidized by the Government or protected by tariffs. The production of potash from wood ashes reached its peak in 1825. Beginning in 1823, a cheaper product, sodium carbonate, made by the Leblanc process, was substituted for much of the potash used in industry. Production rapidly declined after the Civil War, when the forests most productive of potash had become depleted and labor had become

Jan 1, 1949

By David W. Brunton

Mine-drainage and the ever-increasing demand for water on the plains have within the past few years necessitated the driving of a great number of adits and tunnels, including many of considerable size and great length. In most instances, existing conditions have called for extreme rapidity of execution; and this necessity, coupled with the high altitudes at which most of the work has been carried on, excessive freight-rates, and difficulty of access, has involved many complex and interesting problems. One of the most rapidly executed undertakings of this class is the Laramie tunnel, recently completed for the Laramie-Poudre Reservoirs & Irrigation Co. This tunnel is driven through Green ridge, a spur of the Continental Divide, which separates the Laramie river from the Cache-la-Poudre in Laramie county, Colo. Green ridge is extremely persistent, and further northward in Wyoming is known as Sherman hill, the highest point on the Union Pacific railway. At the point where the tunnel is driven, two opposing bends bring these streams within 2.5 miles of each other, with a difference in elevation of 500 ft. The rock exposed on the banks of the two rivers does not differ materially in hardness; and, without a geological study of the conditions involved, it would appear that the difference in the depth of erosion of the two streams is due principally to the greater volume of water at this point in the Cache-la-Poudre, which has a drainage-area above the tunnel-portal of 110 sq. miles, as against 30 sq. miles of natural drainage for the Laramie. To increase the water-supply at the tunnel, however, this latter amount has been augmented by two side collection-canals, which bring the available drainage-area up to 84 square miles. The nearest railroad shipping-point to the eastern portal is

Jan 1, 1913

By C. P. Proctor, J. T. Crawford

TROUGH washers were among the earliest methods used for concentrating ores; they are referred to by Agricola about the middle of the sixteenth century as already being used while the hand- operated jigging sieve had only recently come into use. For cleaning coal the trough washer apparently was first used in France and Belgium .about 1841. The early trough washers were intermittent and the refuse at least was shoveled out by hand. The invention of a continuous jig washer, by a Frenchman, Berard, in 1848, acted as a stimulus to coal washings in jigs and retarded progress in trough washing' in the nineteenth century. Chapman and Mott describe a number of trough washers developed in England and on the Continent from 1850 to 1900, such as the Bell and Ramsay, Ramsay, Bell and Green, Wunderlich, Scaife, McLellan; Lodge, Elliott, Blackett, and Murton. , The later of these removed the refuse mechanically, either intermittently or continuously, but in ways that interfered with stratification. THE RHEOLAVEUR A Belgian engineer, Antoine France, is responsible for the development of means to remove refuse materials continuously from a trough washer while preserving stratification and preventing the loss of coal with the refuse. The methods and equipment devised, which have become known throughout the world as Rheolaveur, were initiated at the St. Nicholas mine near Liége, Belgium, about 1912. This installation consisted of two units to wash 20 to 8-mm. (13/15 to 5/16 in.) and 8-mm. to 0 (5/16-in. to 0), each having only two superimposed inclined troughs. The first few "Rheo" boxes on the top trough removed refuse directly and the remaining Rheo boxes discharged impure refuse to the lower trough for rewashing. On the lower trough the first few boxes removed refuse and the following boxes removed a middling product

Jan 1, 1943

By Kirtland Marsh

THE manufacture of gas masks by the Chemical Warfare Service, U. S. A., required preparation of the carbon used in the canisters. The largest plant for the production of this carbon was situated at the works of the Astoria Light, Heat and Power Co., at Astoria, N. Y.; this paper will deal1 with the pyrometry equipment at that plant. Commercial charcoal was found unsuitable for use in gas masks because of its low power of absorption and its poor resistance to abrasion. The best raw material for the production of carbon was found to be coconut shells, but any kind of nut shells or fruit pits were used when sufficient quantities of coconut shells could not be obtained. The shells were first carbonized in retorts, the carbon was then crushed and screened between 8 and 16 mesh, and finally submitted to a special heat-treatment in air; steam treatment was later substituted for treatment in air. The production of gas-mask carbon on a commercial scale was begun at Astoria about Aug. 1, 1917. Temperature control was essential during the initial carbonization of the shells, as well as during the air or steam treatment, and pyrometers were installed for this purpose. The installation and maintenance of all pyrometry equipment was done by the pyrometry department, consisting of an officer in charge, an assistant, and two men. A special pyrometry laboratory was maintained in which all repairs were made.

Jan 9, 1919

By M. C. Flemings, T. S. Piwonka

Pore formation is examined analytically in cellu-larly solidified single crystals, in cylindrical castings of pure metals and alloys, and in unidirectionally solidified castings. Effects are considered of fluid flow. dissolved gas, and surface tension. Experimental results show that flow through a partially solid "mushy" aluminum alloy obeys relations similar to those applicable for flow through other types of porous beds. Flow rate is proportional to the square of the fraction liquid (fL) for fL less than 0.3. Results indicate models chosen for mathematical description of pore formation in alloy solidification are valid. ONE of the solidification variables which is influential in determining mechanical properties of castings and of wrought material produced from cast ingots is porosity. This porosity may result from shrinkage, dissolved gases, or a combination of both, and may take the form of either macroscopic pores in localized areas of the casting or microporosity evenly distributed throughout large areas of the casting. In alloys which freeze over a range of temperatures some microporosity is generally found after solidification. There has been much discussion as to whether the micropores are caused primarily by shrinkage, by gas, or by a combination of both.'-3 There has, however, been little experimental or analytical work performed to delineate the relative contributions of shrinkage and gas in causing microporosity or to quantitatively describe the influence of processing variables on microporosity. Porosity other than microporosity (e.g., center line shrinkage) has also received only limited quantitative treatment.495 The aim of this work is to examine analytically the general problem of pore formation in solidification and to perform limited confirmatory experiments. Consideration is first given to shrinkage porosity in pure and nearly pure metals (shrinkage in cellular growth, centerline shrinkage in cylinders). Next, a discussion is given of formation of shrinkage-caused microporosity in unidirectional solidification and in "mushy" solidification. Finally, influences of dissolved gas and surface tension on microporosity are examined. Numerical results are given for aluminum and an aluminum alloy. Typical examples of microporosity are shown in Figs. 1 to 3, for 1) cellularly solidified aluminum, 2) sand-cast aluminum alloy, and 3) low alloy steel. SHRINKAGE POROSITY IN PURE AND NEARLY PURE METALS 1) Cellular Growth. In cellular freezing of an impure liquid, liquid grooves may exist over a considerable length of the growing crystal.6 The cross-sectional area of the grooves decreases with increasing distance from the cell tips; the root of the groove is blunt if the liquid at this point reaches eutectic composition. As a result of volume contraction during solidification, flow occurs down the groove, parallel to the growth direction; hence, there must be a pressure drop from the groove entrance to points within the groove. The geometry of the groove is simplified to that of a circular cylinder of radius r and length L, Fig. 4, L » r, and a simple and useful limiting case is obtained. This is that, in the circular cylinder freezing at constant velocity, the pressure at the root of the groove is lower than that pressure at radius r in grooves of other geometries where r decreases continuously to a lower limit at L. As discussed below, a pore resulting from a given pressure difference

Jan 1, 1967

By C. S. Matthews, P. Hazebroek, H. Rainbow

It ha been suggested that lormation fractures created by well stimulation treatments will adversely affect sweep-out efficrency in injection operations. Fluid-flow model studies involving vertical fractures of various lengths and fluid systems of various mobility ratios have been carried out to study this subject. In addition, limited data have been obtained on one model containing a horizontal fracture. It was found that relatively long and highly conductive fractures (not generally obtained fracturing operations) were required to affect the sweep-out efficiency substantially. In a given case in the field an approximate distinction can be made between the presence of long conductive fractures and shorter or less conductive ones. This is done with pressure build-up analyses along with data on the relationship of fracture length and conductivity to well productivity. This type analysis shows that usually the fractures induced are either short or of limited conductivity and therefore do not damage sweep-out efficiency. INTRODUCTION Improved well productivity and in-jectivity can frequently be exploited in injection operations. Higher total throughput can yield improved economics. On occasion, the achievement of an increased productivity or injectivity in specific wells can bring about a more uniform sweep of the reservoir. Higher rates can be exploited particularly in water floods of "depleted" reservoirs where a rapid "fill-up" is desired and where low pressures contribute to low well productivity. The creation of fractures local to the wellbore is an excellent means for achieving these objectives. Even though fracturing has been employed in some floods with success,1"3 there still seems to be some reluctance to employ this tool for fear of undue damage to the flood pattern and ultimate recovery. We therefore need to examine the influence which fractures of varying length may have on flood performance and then determine the length of fractures which obtain in the field with conventional fracture treatments. A substantial influence of fractures on the recovery obtained at breakthrough of the injected fluid has been presented by Crawford and Collins for equal fluid mobilities for the line-drive pattern.4,5 In addition, the influence which a fracture has on the production performance after breakthrough and on the ultimate recovery warrants consideration in reaching a conclusion concerning the use of induced fractures in flooding operations. This report presents this type of data for the five-spot injection pattern for several fluid mobilities. In arriving at some conclusion concerning the fracture lengths obtained in field operations we must examine the performance characteristic most affected by the fracture. This is the change in the flow system as reflected in the change in productivity and pressure build-up behavior. A study of these changes is also presented in this report. RESERVOIR ANALOGS The X-ray shadowgraph technique, employing miscible displacement in porous models, has been used in the study of the influence of fractures on pattern sweep-out efficiency. The X-ray shadowgraph procedure is described in detail in an earlier report8. Fractures were represented by leaving the proper portion of the model surface exposed to either injection or production. This assumes the fracture resistance to be negligible compared to that of the formation. Actually the flow resistance in propped fractures obtained in the field is sometimes not negligible so that the results with this model indicate the maximum influence of the fracture. Two types of models were necessary to represent vertical fractures in a five-spot flood. These pattern elements are illustrated in Fig. 1. In studying the influence of the horizontal fracture, only one well spacing length to thickness ratio of 50 was used. The pool unit of a Carter Electric Analyzer was used in studying the influence of fractures on productivity and build-up behavior. The square drainage system of a well was represented by a network of 576 elements of equal volume and resistance. One-fourth of this drainage area was studied as a model unit using a network of 144 condensers and resistors. Vertical fractures were represented by a shunt directed from the well perpendicular to the drainage boundary. Horizontal fractures were represented by a circular shunt. Resistance of a shunt was varied in representing different conductivities for the fractures. FRACTURE DIRECTION AND LENGTH The direction at which a vertical fracture extends into the formation and its length and conductivity influence the sweep behavior. The two

By Ralph W. M. Lai, D. W. Fuerstenau

This paper presents the results of a study of the principles which control the distribution of ultrafine particles between an oil phase and an aqueous phase. Alkyl sulfonates were used to control the wettability of fine alumina particles and to stabilize the water-isooctane emulsion system in the extraction process. The effects of sulfonate chain length, sulfonate adsorption, pH, and oil-water ratio on the recovery of solids in the oil phase were investigated. Higher extraction was found under conditions which yield higher hydrophobicity and large interfacial area of the oil-water emulsion. Today there is considerable interest in developing methods for the recovery of fine particles from disseminated ores. One such method might be the extraction of fine particulate solids from aqueous suspensions into an oil phase, and one example of a successful industrial process based on oil-water distribution phenomena is the emulsion flotation process used in concentrating manganese ore.' The oil agglomeration process of Farnand, Smith, and Puddington has been suggested for concentrating tin ore. Patents 3-4 for oil flotation processes extend back to that of William Haynes in 1860. The basis of all these processes is directly related to the stabilization of emulsions with solid particles. The first extensive study of oil-water emulsions stabilized by finely divided solids was made by Pickering. Later, Briggs,6 weston, 7 Chessman and King,8 and Leja and Schulman9 experimentally demonstrated how solid particles control water-oil and oil-water systems. Hildebrand10 suggested that fine particles can stabilize an emulsion because the fine particles are partially wettable by both oil and water, that is, that the contact angle must be finite. Takakuwa and Takamori 11 recently applied emulsion inversion to the study of collector adsorption in flotation systems. At the Royal School of Mines, Shergold and Mellgren12 are currently carrying out a comprehensive study of the extraction of fine particles into an organic liquid phase. In the present study of the liquid extraction or oil flotation of ultrafine particles, the recovery of hydro-philic alumina particles of 0.1-µ average diameter was determined after separating an isooctane-water mixture (emulsion) into its two phases. Alkyl sulfonates of different chain lengths were used to change the wettability of the alumina and to effect emulsifi-cation of the oil-water mixture. The effects of the oil-water volume ratio, sulfonate adsorption, and pH on the recovery of the fine particles were investigated. Since the surface charge on an oxide such as alumina is determined by the adsorption or interaction of H+ and OH- with the surface, pH control is extremely important. Furthermore, since the zero point of charge (zpc) of alumina13-14 occurs at pH 9 to 9.4, major adsorption effects with anionic collectors in these systems will occur below pH 9. The results of the foregoing investigation are discussed in terms of the recovery of the fine particles, the oil-water ratio, contact angles, surface tension, the adsorption of sulfonate onto the solid surface, and the emulsifica-tion of oil. MATERIALS AND EXPERIMENTAL METHODS Materials: The particulate solid used in all the experiments was Linde "A" alumina, a high-purity, readily available form of a-alumina. The surface area of the alumina, as evaluated from measurements of stearic acid adsorption from benzene, was 14.5 sq m per gm, based on a value of 20.5 sq Å for the cross-sectional area of stearic acid.13 All aqueous solutions were prepared from triply distilled conductivity water. Other materials included high-purity crystals of sodium alkyl sulfonates, isooctane, and, for pH adjustments, reagent grade hydrochloric acid and sodium hydroxide-Because sulfonic acids are strong acids, they are

Jan 1, 1969