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By J. G. Bartram

Jan 1, 1934

By T. P. Floridis, J. H. Young

The need for close control of the phosphorus content of steels has led to numerous investigations on the equilibria of the dephosphorization reactions. Winkler and chipman1 have established the general conditions for effective dephosphorization of steel. They are high slag basicity, high oxygen potential, and low temperature. Other investigators have made additional contributions to the understanding of the dephosphorization process. The current status of the understanding of the dephosphorization of steel is concisely presented by Bodsworth2 and by Ward. The investigation reported in this communication was undertaken with the purpose of establishing the effect of additions of barium oxide and calcium fluoride on the dephosphorizing capacity of slags. Esin and Gel'd4 proposed that barium oxide, being more basic than calcium oxide, should cause an increase in dephosphorizing capacity when added to steelmaking slags, or when used as a substitute for calcium oxide. Derge5 has also proposed that in the future conventional slags might be replaced by BaO-Al2O3 slags. There is, however, no experimental evidence confirming the effect of barium oxide on the dephosphorizing capacity of slags. The effect of calcium fluoride on the dephosphorization of steel is not clearly understood. It is generally recognized that additions of calcium fluoride are beneficial. It is not clear, however, whether calcium fluoride affects the equilibrium of the dephosphorization reaction, or whether it simply causes an increase in the fluidity of the slag and, consequently, faster approach to equilibrium. The experimental procedure consisted in equilibrating synthetic molten slags with liquid copper at 1550°C under a gas stream containing argon, hydrogen, and water vapor. In all experiments the argon to hydrogen ratio was approximately 4:1, and the hydrogen to water ratio was 5.42:l. Molybdenum crucibles were used as containers for the slag and metal. Under the above-described conditions of temperature and composition of atmosphere, there was no observable attack of the crucibles by the metal, slag, or atmosphere. Copper was used instead of iron, because iron attacks molybdenum. The equilibration was made in a tubular furnace consisting of a recrystallized alumina tube. The alumina tube was heated by electrical resistance. A Pt-40 pct Rh wire winding was used for most runs. A silicon carbide tubular resistor was also used for some runs. Temperatures were measured with a Pt-Pt-Rh (10 pct Rh) thermocouple and kept constant within ±5°C. Equilibrium was approached from both sides, i.e., by adding the phosphorus either as oxide in the slag or as a phosphorus-rich alloy of phosphorus and copper. The holding time at the equilibrium temperature was 6 hr. At the end of each run the crucibles were rapidly cooled and removed from the furnace. The slag and metal were separated and analyzed. The experimental results are shown in Table I. The phosphorus content of the slag is expressed both as percent phosphorus pentoxide and as percent phosphorus. The basicity ratio is computed by dividing the number of moles of basic oxides-oxides of barium, calcium, magnesium, and sodium—by the number of moles of acidic oxides- oxides of aluminum, phosphorus, and silicon. Calcium fluoride is not included in the computation of the basicity ratio; i.e., calcium fluoride is assumed to be neither basic nor acidic. The distribution ratio of phosphorus—percentage of phosphorus in the slag divided by the percentage of phosphorus in the metal- is plotted in Fig. 1 against the basicity ratio. The results indicate that slags containing barium oxide have greater dephosphorizing capacity than slags containing calcium oxide. The high dephosphorizing capacity of slags containing sodium oxide and the low dephosphorizing capacity of magnesia-containing slags which already have been reported in the literature2 are confirmed by the results of this investigation. It appears that calcium fluoride has a beneficial effect on the distribution of phosphorus between slag and metal in acid slags only. Although the obtained distribution ratios between the phosphorus contents of slag and copper are not directly applicable to the dephosphorization of steel, they are sufficient for evaluating the effect of slag additions on the dephosphorizing capacity of slags in general. An increase in the ratio of distribution of phosphorus between slag and metal indicates lowering

Jan 1, 1968

"Located on the Big Hole River, three miles from Divide, Montana, and 21.75 miles from Butte.Built in 1899.DAM: Rock-filled wooden crib, 512 ft. long and 57.5 feet high.SPILLWAY: Equipped with flash-boards 189 ft. long, 8 ft. 10 inches high.PENSTOCKS: Two 8 ft. diameter of steel, each branching and supplying two wheels.WHEELS: Four double horizontal, double discharge turbines, made by The James Leffel & Co., 1,000 h-p., 180 r. p. m., direct connected to generators, operating at 60 ft. head. GENERATORS: Four G. E., revolving field, 750 k-w., 180 r. p. m., 800 volt, 3 phase, 60 cycle alternators.EXCITERS: Two water-wheel driven exciters.TRANSFORMERS: 12 250-k-w. G. E. air blast, primary 15,000 volts, Secondary 800 volts.OPERATION: The plant operates essentially as a peak load plant. Except in flood period, there is insufficient water to operate at full load continually. In December its average output is about 500 k-w."

Jan 1, 1913

By William R. Webster

At the Richmond mecting in February, 1901, I presented for discussion the proposed rail-specifications of Committee No. 1 of the American Section of the International Association for Testing Materials, with a review of their work, and other matters relating to the heat-treatment and chemical composition of steel (Trans., xxxi., 455). In order to bring out the views of our members on the important points referred to, I offered for discussion the following questions and comments (trans., xxxi., 972): " 1. The advantages to be gained by using more metal in the flanges and web of the heavier sections of rails.

Jan 1, 1903

By Edward B. Durham

At the Richmond mecting in February, 1901, I presented for discussion the proposed rail-specifications of Committee No. 1 of the American Section of the International Association for Testing Materials, with a review of their work, and other matters relating to the heat-treatment and chemical composition of steel (Trans., xxxi., 455). In order to bring out the views of our members on the important points referred to, I offered for discussion the following questions and comments (trans., xxxi., 972): " 1. The advantages to be gained by using more metal in the flanges and web of the heavier sections of rails.

Jan 1, 1903

By M. J. Sheriff, D. H. Smith, W. Macdonald

The paper outlines the basic procedure used in electrical system planning and design. Consideration is given to the use of applicable codes and standards, development and use of a system One Line Diagram, power availability, load requirements and power factor. Also discussed are the factors influencing the selection of power supply and distribution arrangement, voltage levels, system grounding, distribution and utilization equipment such as switchgear, transformers, motor control, cable systems, motors. Short circuit calculation methods and system protection are discussed.

Jan 1, 1978

By J. B. Austin

It is now well established, chiefly through the work of Davenport and Bain,' that the influence of temperature upon the rate of transformation of austenite to ferrite at constant temperature is represented by a curve of the type shown in Fig. 5 on page 295 and the reasons for this general shape have been discussed by them in a qualitative way. Thus, the upper part, or nose, of the curve is the resultant of two factors of which the rate of change with temperature is not the same, and by analogy with other like cases it is almost certain that these factors are: (1) the chemical potential, or driving force, of the transformation, which is zero at the equilibrium temperature and increases rapidly as the temperature falls below this point; and (2) a factor analogous to viscosity, or resistance of the crystal lattice to a change in structure, which also increases as the temperature is lowered. Just below the equilibrium temperature this virtual "viscosity" of the metal is relatively low—that is, the metal offers little resistance to a change in lattice—but the driving force is also small, and the net result is that the reaction proceeds slowly. As the temperature is lowered the magnitude of both factors increases; but at first the driving force increases more rapidly than the resistance and the reaction is observed to proceed more rapidly. At lower temperatures, however, the resistance begins to increase faster than the driving force, and eventually, at the nose of the curve, overbalances it, causing the reaction to proceed more and more slowly thereafter. This concept is somewhat, though not completely, analogous to that employed in certain electrical cases where the precise factors are known and are separately measurable. The current I (in amperes or coulombs per second) flowing through a given wire is proportional to the impressed potential, or driving force E, and is inversely proportional to the resistance R of the wire; that is, I = E/R. Stated in a slightly different way, the time required for one coulomb to pass a given point (1/I) is equal to R/E. If the temperature of the whole circuit is changed, the resultant change in 1/I will depend on the relative rates of change of R and of E,

Jan 1, 1935

By J. B. Austin

It is now well established, chiefly through the work of Davenport and Bain,' that the influence of temperature upon the rate of transformation of austenite to ferrite at constant temperature is represented by a curve of the type shown in Fig. 5 on page 295 and the reasons for this general shape have been discussed by them in a qualitative way. Thus, the upper part, or nose, of the curve is the resultant of two factors of which the rate of change with temperature is not the same, and by analogy with other like cases it is almost certain that these factors are: (1) the chemical potential, or driving force, of the transformation, which is zero at the equilibrium temperature and increases rapidly as the temperature falls below this point; and (2) a factor analogous to viscosity, or resistance of the crystal lattice to a change in structure, which also increases as the temperature is lowered. Just below the equilibrium temperature this virtual "viscosity" of the metal is relatively low—that is, the metal offers little resistance to a change in lattice—but the driving force is also small, and the net result is that the reaction proceeds slowly. As the temperature is lowered the magnitude of both factors increases; but at first the driving force increases more rapidly than the resistance and the reaction is observed to proceed more rapidly. At lower temperatures, however, the resistance begins to increase faster than the driving force, and eventually, at the nose of the curve, overbalances it, causing the reaction to proceed more and more slowly thereafter. This concept is somewhat, though not completely, analogous to that employed in certain electrical cases where the precise factors are known and are separately measurable. The current I (in amperes or coulombs per second) flowing through a given wire is proportional to the impressed potential, or driving force E, and is inversely proportional to the resistance R of the wire; that is, I = E/R. Stated in a slightly different way, the time required for one coulomb to pass a given point (1/I) is equal to R/E. If the temperature of the whole circuit is changed, the resultant change in 1/I will depend on the relative rates of change of R and of E,

Jan 1, 1935

By G. H. Matheson, J. M. W. Mackenzie

The coal concentrates studied contained clay slimes which would not flocculate on the addition of a polymer flocculent alone. The mechanism of the flocculation process is interpreted on the basis of the flocculation of lyophobic colloids. The filtration rate characteristics are shown to deviate slightly from certain basic filtration equations. Cake moisture was shown to decrease with cake drying time and vacuum, and increase with cake thickness. Filtration is a commonly accepted method of dewa-tering the fine coal concentrates produced in coal cleaning operations. Dewatering of these concentrates, using drum or disc vacuum filters, usually presents few technical difficulties and will result in the production of a filter cake containing some 20 to 25 pct moisture. In many coal cleaning operations it is common practice to add flocculants to the coal concentrates prior to filtration to increase the filtration rate. The mechanism whereby flocculation increases filtration rate has been summarized by Gaudin,4 while Geer, et a15 have compared the effectiveness of starch and synthetic flocculants as filter aids for a variety of coal concentrates. Coal concentrates, containing appreciable quantities of expanding lattice clays of the montmorillonite-illite group, sometimes prove impossible to filter without flocculation of the pulp prior to filtration. The fine coal concentrates produced at the Newcastle washery of The Broken Hill Proprietary Co. Ltd. fall into this group. Coals mined in this district contain appreciable quantities of expanding lattice clays which break down in the washery circuit waters and, by processes of mechanical inclusion, contaminate the coal concentrate thickener feed. Despite the classifying action of this thickener, the underflow which is pumped to the filters contains sufficient clay slimes to render filtration of the unflocculated pulp impossible. Filtration leaf and plant tests were carried out to develop effective and economic flocculant combinations and to determine the filtration characteristics of the flocculated coal concentrates. The determination, by leaf testing, of the filtration characteristics, and the analysis of these characteristics in the light of the equations of Brown2 resulted in the successful trial operation of the filters in the Newcastle washq. Although the filtration characteristics are not entirely in agreement with the theoretical treatment of Brown, the equations developed made it possible to predict, from leaf tests, the effect in the plant filters of pulp density, form vacuum, and form time on filtration rate and filtrate volume. EXPERIMENTAL PROCEDURES The sample used for leaf testing was the coal concentrate thickener underflow, which in plant operations would form the feed to the two 12-disk Dorr-Oliver filters. The feed to the coal concentrate thickener comprises the undersize produced by dewatering the Diester table concentrate on 5-mm dewatering screens and the overflow produced by cycloning of the froth flotation concentrate. At the time of testing these filters were inoperative because of the difficulties in filtration, arising from contamination of the

Jan 1, 1962

By Ernest Stütz

(New York Meeting, October, 1913.) THE problem of increasing blast-furnace efficiency through diminution of flue-dust production while operating with burdens consisting largely of fine ores has of recent years attracted the attention of metallurgists, whether directly or indirectly interested in the economies of iron smelting, and the various methods evolved from theory or practice have been. submitted to wide discussion. After the very thorough and, at that time, exhaustive view of the whole subject, which was afforded to the industry by the meeting of this Institute in February, 1912, the subject was again taken up at the meeting of the Verein deutscher Eisenhüttenleute at Düsseldorf in December, 1912. While American and German conditions are not entirely identical, it may be of interest to give here the words of the gentleman summing up the discussion at the Düsseldorf meeting : ?The chief advantage offered by the use of briquettes lies in the fact that disturbances in the furnace, caused mostly by the presence of fine ores in the burden, are avoided, and that blast pressure can be considerably reduced. The resulting economies cannot be overrated, as, with lower blast consumption per ton of product, the installation will be able to take care of increased production. In consequence of lower pressure and speed of blast, heat is more efficiently utilized,, flue gas temperature is lowered, and coke particles are less liable to be carried along with the flue dust, of which considerably less is produced. Finally, by increased regularity of operation and higher temperature in the lower parts of the furnace, the quality of the product is improved. The question of briquetting iron ores has grown to be one of the most important in the iron industry, and it is not any more a question of what is the cost 'of briquetting a ton of ore, but what, in. using ore briquettes, is the cost, of: production of a ton of iron."

Jan 7, 1913

By Ernest Stütz

(New York Meeting, October, 1918.) THE problem of increasing blast: furnace efficiency through diminution of flue-dust production while operating with burdens consisting largely of fine ores has of recent years attracted the attention of metallurgists, whether directly or indirectly interested in the economies of iron smelting, and the various methods evolved from theory or practice have been submitted to wide discussion. After the very thorough and, at that time, exhaustive view of the whole subject, which was afforded to the industry by the meeting of this Institute in February, 1912, the subject was again taken up at the meeting of the Verein deutscher Eisenhüttenleute at Diisseldorf in December, 1912. While American and German conditions are not entirely identical, it may be of interest to give here the words of the gentleman summing up the discussion at the Diisseldorf meeting: ' The chief advantage offered by the use of briquettes lies in the fact that disturbances in the furnace, caused mostly by the presence of fine ores in the burden, are avoided, and that blast pressure can be considerably reduced. The resulting economies cannot be overrated, as, with lower blast consumption per ton of product, the installation will be able to take care of increased production. In consequence of lower pressure and speed of blast, heat is more efficiently utilized, flue gas temperature is lowered, and coke particles are less liable to be carried along with the flue dust, of which considerably less is produced. Finally, by increased regularity of operation and higher . temperature in the lower parts of the furnace, the quality of the product is improved. The question of briquetting iron ores has grown to be one of the most important in the iron industry, and, it is not any more a question of what is the cost of briquetting ton of ore, but what, in using ore briquettes, is the cost of production of a ton of iron.'

Jan 7, 1913

By Thomas A. Simpson, Russell A. Walker

Hydrogeological techniques were used to solve problems of slope stability in open-pit mines of the Eufaula bauxite district, Ala. Geologic and hydrologic data were evaluated and used to design a system of dewatering wells to enable the operators to mine bauxite more efficiently and economically. Walls of open-pit mines in the district were subsequently stabilized by the operation of the dewatering system. Three open- pit mines, each at varying stages of the mining process, of the A.P. Green Refractories Co., were used to develop a sequential series of guidelines that indicate how to effectively remove ground water from the formations surrounding the ore bodies in the district. The use of sound engineering principles in well design, in combination with the correct interpretation of the pit hydrology provided the basis for solutions of the slope-stabilization problem and aided in the economical removal of bauxite from mines of the district.

Jan 1, 1976

By John Dasher, M. C. Chang

The Crucible mine in Pennsylvania, operating on Pittsburgh seam coal, is rated at 5000 tpd. The washing plant, built in 1943, is rated at about 400 tph, using hydroseparator boxes to wash the coarse coal (4 x 5/16 in.) and hydrotator units for the fine coal (5/16 x 0). It is generally acknowledged that gravity concentration equipment cannot be used efficiently to beneficiate coal finer than about 65 mesh. Before the present flotation circuit was installed, Crucible recovered its fine coal slurry, predominantly -24 mesh material, by passing it through a battery of five 14-in. and one hundred and ten 3-in. Hey1 & Patterson cyclones in parallel with a 75-ft Dorr thickener. About two thirds went to the cyclones and one third to the thickener. Underflows from cyclones and thickener were filtered, respectively, in one 12-disk Eimco and two 4-disk Oliver filters fitted with stainless steel cloth. The resulting cakes were added to the coarse metallurgical coal. The filtrates, overflow from the 3-in. cyclones, and thickener overflow were recycled to the coarse coal plant.

Jan 3, 1959

By B. C. Allen

Surface free energy and surface self-diffusion of solid molybdenum were studied in the temperature range 1600" to 2400°C using pressure-sintered bi-crystals. Comparison of groove angles formed in various surfaces perpendicular to the grain boundary indicate a maximum of 1 pct variation in surface free energy with crystallographic mientation. This anisotropy tends to decrease with increasing temperature. The surface diffusion of the bicrystals is equivalent to that of sheet with a mild (100) Preferred orientation. Anomalously low values found for bi-crystals with surface orientations of (OOl), (012), and (011) are rationalized in terms of anisotropy in surface free energy. THE effect of crystallographic orientation on surface free energy1,' and surface self-diffusion3,4 has been primarily studied in fcc metals. The object of this work was to study the effect of orientation on surface diffusion and surface free energy of bcc molybdenum using pressure-sintered bicrystals. EXPERIMENTAL WORK Materials and Crystal Preparation. Arc-melted molybdenum rod was obtained commercially and electron beam zone refined at 50 cm per hr at 10- 5 torr to form single crystals about 8 cm long and 0.65 cm diam. Three crystals were prepared with axial orientations about 1 deg from [001.], [011], and. [111]. To reduce the carbon content, the crystals were annealed 2 hr in 1.4 atm flowing wet hydrogen at 2050°C. Then the oxygen content was reduced by annealing for 2 hr in -30°C dewpoint hydrogen at 2020°C. The resulting impurity analysis is given in Table I. Bicrystal Preparation. The single crystal rods were cut into transverse slices with a thin silicon carbide abrasive wheel to produce specimens about 0.6 cm long. They were mounted in epoxy and surrounded by stainless steel washers. Cutting in half was done longitudinally at various angles to known crystallographic planes containing the cylinder axis according to Fig. 1. To reduce surface deformation resulting from the cutoff wheel and thus reduce parasitic grain boundary formation on subsequent annealing, about 0.003 cm was manually ground off each cut surface with 600 grit paper. Care was taken to keep the surface flat. After removal from the mounts, one half was generally ro-tated 180 deg with respect to the other to give a po- tential symmetrical tilt grain boundary between the two halves. In the other cases when low misorienta-tion angles were desired, the crystals were not rotated. On the basis of symmetry, sufficient bicrystals were prepared to cover the entire range of misorientations for symmetrical tilt boundaries. The misorientations, +, ranged from 0 to 45, 0 to 90, and 0 to 60 deg for [001], [011], and [111] bicrystals, respectively. One [Ill] twist bicrystal was prepared from 2 single crystal discs rotated 17 deg relative to each other. Each specimen consisted of two pieces which were placed in a cylindrical tantalum can. Sharp edges were rounded and the fit was made as snug as possible to reduce subsequent deformation during bonding. The assembly and crystals generally were vicuum outgassed at 900" or 1700°C and then electron beam welded in the can at l x 10-4 torr. After being leak checked, the samples were placed in an autoclave and hydrostatically gas-pressure bonded5 in four batches under helium at 10,000 to 18,000 psi at 1650°C for 3 hr. Satisfactory bonds were obtained in many cases, and most of the crystals bonded after two exposures. The results did not appear to be affected by the various pressures used, preannealing conditions, crystal orientation, or time-pressure-temperature route taken to the final bonding condition. After bonding, the tantalum cans were selectively removed in cold concentrated HF. Measurements indicated overall deformation was under 1 pct. The bicrystals were metallographically ground and polished flat and perpendicular to the axis. Examination showed the boundaries were straight and almost free of parasitic grains caused by extraneous local deformation. Annealing. In preparation for thermal grooving, the bicrystals were cleaned and annealed by outgassing at 10-5 torr at 1900°C and heating at 2300°C under 1 atm 99.996 Ar for 0.5 hr. The crystals were held in a closed 4-deck box made of molybdenum sheet, and were heated in a Ta-1OW resistance furnace. The ar-

Jan 1, 1970

By Joseph S. Malesky

The discovery and development of explosives mark one of the most important findings in the history of civilization. Without explosives our vast economic enterprise concerning the mining of coal, copper, iron, aluminum, and various other ores could not function. Explosives are used in all kinds of construction works, in the razing of old buildings, blasting of trenches, driving of tunnels, and in many other instances common to our everyday life. For these reasons explosives are rightfully referred to as the forerunner of progress. An explosive may be defined as a substance (usually a mixture) that, when flame or shock is applied, yields readily to rapid combustion or oxidation, accompanied by the formation of such relatively large quantities of gases as to produce much violence and pressure which, in turn, react against their surroundings and cause what is termed an explosion. By their very nature the action of explosives is destructive and disruptive of adjacent materials. Decomposition of explosives can occur through deflagration, which is rapid burning or combustion, as in the case of black powder, or through detonation, which is an almost instantaneous disruption, as in the case of dynamites and blasting agents. HISTORY OF BLASTING WITH EXPLOSIVES At one time workmen obtained stone blocks for building by grooving the rock with crude picks, driving wooden wedges into niches in the rock, and pouring water on the wedges; the swelling of the wood forced out the blocks. As late as the 17th century, fires were placed against the face of rock to crack it, and water was sometimes dashed on the heated rock to shatter it by sudden cooling. The progress of our country is synonymous with advancement of the improved manufacture and extended use of explosives. Coal had been

Jan 1, 1981

By R. H. Migliaccio, M. B. Kahle

The railroad haulage system was started at Kennecott's Bingham Mine in 1906 and has remained a prime mover of ore and waste for the succeeding sixty years. As the stripping ratios increased contract stripping on the upper levels of the mine was introduced employing truck and shovel methods. The ore production then was 90,000 tpd. Analysis of expanding the ore production to 108,000 tpd revealed that the increased ore production and continually rising stripping ratio would result in waste production requirements that exceeded the capacity of the rail haulage system above 6290 level. The advent of larger haulage trucks (65-100 tons) in the early 1960's made available to the Bing- ham Mine economic and operating factors which showed truck haul- age to be the best replacement for rail haulage on the upper levels of the mine. As part of that analysis it was concluded that company stripping would replace the contractor stripping in the top area of the mine.

Jan 7, 1973

By W. C. Hagel, J. H. Westbrook

THERE has been a recent revival of interest in the intermetallic compound AgMg as an experimental material for study of the physical and chemical properties of simple ordered structures. Studies of mechanical behaviors,1-4 diffusion,5,6 and thermo-dynamic properties7'8 have been reported. In several of these studies, heat treatments have been carried out in argon-filled silica capsules at temperatures as high as 750°C with no apparent adverse effects. The present authors were, therefore, startled to discover in the course of some yet unpublished work, that gross melting of near-stoichio-metric AgMg compositions occurred in such samples more than 100 deg below their melting point of about 800°C. This note is to report a brief series of experiments carried out to establish the reason for this behavior. Gross errors in sample composition and failure of furnace temperature controls were quickly eliminated as causes of melting. The first tangible lead came from chemical analysis of an AgMg sample which had melted during treatment at 750°C. A silicon content of 3.3 wt pct was found. Since satisfactory analyses had been obtained on the original as-cast ingot, contamination by diffusion and/or reaction with the fused silica capsule seemed a distinct possibility. A perplexing fact, however, was the apparently capricious incidence of the effect. Not only was it previously unknown, even in the experience of the present authors; but, in the early part of the present study, melting sometimes occurred and sometimes not with specimens treated under constant conditions. Indeed, one sample successfully survived a 750°C heat treatment and yet melted completely during the course of a subsequent anneal in an identical capsule at a lower temperature. To obtain evidence that silicon contamination could lower the melting point to the extent observed, the following experiment was performed. A series of ternary alloys was made up with a stoichiometric AgMg base and containing 0.1, 0.2, 0.4, 1, 2, and 4 wt pct Si. Melting was done in MgO crucibles under a cover of argon gas. After holding 10 to 20 min in the temperature range 850° to 900°C, the alloys were allowed to solidify in the crucible and the temperature during cooling automatically recorded with a Pt/Pt-10 Rh thermocouple. Results from the cooling curves are shown in Fig. 1. Checks within 2 to 5C° were obtained upon repeated melting, cooling, and freezing. The whole series of cooling curves as well as metallographic examination of the melted alloys established that the AgMg rich portion of the AgMg-Si quasibinary is an eutectic-type system. The melting point of AgMg is lowered from approximately 820°C in the pure stoichiometric binary9 to about 710°C in the saturated intermetallic phase. Since second phase was observed in all samples on cooling to room temperature, the solid solubility of AgMg for silicon evidently falls rapidly with decreasing temperature as indicated schematically by the dashed solvus in Fig. 1. It is thus established that a silicon content

Jan 1, 1963

By R. D. Pehlke, J. V. Gluck

A study was made of' the effects of up to five additional solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450" to 650°C. The experimental measurements were made in a multielectrode galvanic cell apparatus employing fused LiCl-KCl as the electrolyte. The solute additions included indium, lead, tin, cadmium, copper, silver, antimony, or gold. A range of positice and negative interactiotls with zinc was covered. The experinzer~tal observations were cowlpared with the activity coefficients calculated usitlg either Wagner's first-order Taylor series rnodel or a proposed second-order solution itrteraction model. hi general, the truncated first-order Taylor series proposed by Wagner gaue good results for "dilute" solutions (XBi > 0.90) contaitzing up to six solutes. The second-order model, which includes a second-order cross-interaction term, produced a slight improvement in predictions for solutions with XZn = 0.015 and a significant improvement for solutions with XZn = 0.050 hear the limit of Henry's law region). Seveval of the quaternary solutions studied contained a total solute content of 0.215 mole fraction, and fairly good success was achieved in predicting the activity coefficient 01- zinc. ThE study of thermodynamic interactions between dilute solutes in liquid metallic solutions has occasioned much recent interest. It is useful to recall in this respect that Wagner's well-known expression for the activity coefficient' is a practical application of the problem of representing a given function, i .e., In ?, by means of a sequence of polynomials. No specific physical model of a solution is involved in its use. As suggested by Wagner, a Taylor Series is used to expand In ? about a point of infinite dilution with respect to all solutes. The partial differential coefficients of the series have been termed "interaction parameters". Various authors'-6 have proposed formalisms for parameters, the definitions being designed to meet some specific experimental or physical condition. A usual assumption is that terms above first-order in the Taylor Series may be neglected. In that case, the logarithm of the activity coefficient is expressed as a linear function of solute concentrations. The resulting expression is presumed valid for any number of additional solutes as long as the solution can be regarded as "dilute". This assumption can be termed "the hypothesis of additivity". However, experimental tests of that hypothesis for quaternary or higher-order solutions have been extremely limited. Primarily such tests have been confined to studies of effects of added metallic elements on either the activity of carbon or the solubility of gases in liquid iron.7-13 The only known previous study of an all-metal system is the limited work of Okajima and pehlke14 on the effects of multiple solute additions on the activity of cadmium in liquid lead. The present investigation is a portion of the work to determine the effects of various solute additions on the activity of zinc in dilute solution with molten bismuth in the range 450" to 650C It was shown for such ternary solutions that second-order Taylor Series terms could be evaluated at the same time as first-order terms, with no additional experimentation required. A second-order solution model was described which, under certain conditions, is a rigorous representation of solute activity in a ternary solution. (In the sense employed in this paper, the term "model", as distinguished from "equation", is taken to mean an empirical correlation or formalism, but not a hypothetical physical system per se.) Presumably such a model could be extended to produce a better representation of In ? in solutions of even higher order. The feasibility of a generalized Taylor Series approach to solution interactions and inclusion of second-order terms also has been discussed recently by Lupis and Elliott in independent work concurrent with the present investigation. In addition, they discussed empirical means of estimating certain second -order coefficients.17 The utility of such solution models rests on the ability of a truncated series to represent adequately the experimental facts in multicomponent solutions. Questions that arise include: Do the second-order terms really make a significant contribution? How far away from "dilute" solution may such models be applied? Are the types and varieties of the additional solutes important? among others. In order to provide some answers to these questions, an experimental study was made of the effects of two or more additional solutes on the activity of zinc in dilute solution with molten bismuth. Comparisons were then made with calculated activity coefficients obtained using the previously determined ternary interaction parameters. INTERACTION MODELS As an example of the approach to defining activities in multicomponent solutions, consider the Taylor Series expansion for a quaternary system, i.e., three dilute solutes. Writing terms through second order, the result is:''

Jan 1, 1968

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969

By Y. Fukunaka, Y. Kondo, Z. Asaki, S. Nakashita

The pyrite smelting process in which about half amount of sulfur is recovered from pyrite by thermal decomposition in an oxygen-free high-temperature combustion gas flow in the flash smelting furnace is being conducted at Kokkola Works in Finland. A mathematical model of this process was developed, and the rates of thermal decomposition and fusion of suspended sulfide particles in the reaction shaft of furnace was calculated. This model is thought to be appropriate because of a fairly good coincidence of the calculated length of reaction zone with the shaft height of the furnace at Kokkola Works. The calculated reaction zone in which the thermal decomposition and fusion of sulfide particles occur becomes longer when pyrite particles of larger sizes are fed. The feeding rate of pyrite particles and the gas velocity at the nozzle exit are also the important operating factors. These two factors are closely related to the volume fraction and the residence time of suspended particles in the gas stream, and the optimal combined levels of these factors at which the length of reaction zone becomes minimal were obtained.

Jan 1, 1976