Search Documents

By William M. Baldwin, T. S. Howald, A. W. Ross

EXPLORATORY WORK THE related subjects of preferred orientation, directionality in physical properties, and earing tendencies of wrought metal [ ] strip have attracted the attention of metallurgists to such an extent that in the past 20 years hundreds of researches have been published on this one general problem. The anisotropy of tensile strength and elongation have been exhaustively studied in their relationship to the occurrence of ears in cups drawn from strips-20.29 and, to a lesser extent, yield strength7,11,17 and stress-strain curves" have been investigated. Despite the tremendous fund of knowledge thus accrued, no simple quantitative correlation of directionality and earing tendencies has yet been found. In a sense, this is not surprising. The formation of ears in a drawn cup clearly is a special phase of the general study of metal flow; in particular (as will be brought out in the course of this paper), ears are due to anistropy in the rates of deformation of the metal in the radial, circumferential, and "thickness" directions of the original blank. It would be difficult to effect a correlation between earing tendency and a property that may be completely independent of the flow of metal, or at best related to metal flow in an exceedingly complex fashion. Yet, it is this correlation that has been attempted; tensile strength and elongation are attributes of metal rupture, a phenomenon that has quite admirably been shown to be distinct from the phenomenon of metal flow,21 while yield strength and stress-strain

Jan 1, 1945

By H. M. Fisher, R. E. Snow, S. C. Sun

RAPID colorimetric estimation of the amount of transparent minerals has been applied success- fully to instream mill products at the cryolite flotation plant of the Pennsylvania Salt Mfg. Co., Natrona, Pa. Apparatus used was a Bausch & Lomb monochromatic colorimeter. The optical assembly of the colorimeter, shown in Fig. 1, passes light from a 6-v, 32-cp, prefocus incandescent lamp through two condensing lenses, a heat-absorbing filter, an aperture-control diaphragm, an interference filter, and a sample container. The light finally strikes a barrier-layer photocell and the output current of the photocell is measured by a galvanometer. The engraved index line of the collective lens, located between the lamp and the galvanometer, is imaged upon the transmission scale of the colorimeter by the galvanometer mirror. Reflected light from the galvanometer mirror, the position of which is determined by the output current of the photocell, enables reading of percent transmission throughout the mineral sample being tested. The colorimeter, Fig. 1, was standardized as follows: 1-The colorimeter was connected to a Sola constant voltage transformer, A, of 6-v output operated from a 110-v ac supply. 2-Turning the toggle switch, C, illuminated the transmission scale, B, and the control knob, D, was adjusted with a blank in the optical system until the hairline on the scale read zero. 3-A No. 430 interference filter, E, was inserted into the filter channel, F. &--A test tube, G, containing 7 cc of distilled water was pressed into the sample space, H, and the fine adjustment knob,

Jan 9, 1954

By J. G. Koenigsberger

The electrical specific resistance of rocks in the field is measured by sending a current through a medium of great volume, compared to the electrodes, whose resistivity should be measured. The whole resistance can be determined by the Wheatstone bridge and the specific resistance calculated by a well-known formula. The resistivity of some rocks in place in Germany and in Switzerland is given; first, of a rock near the surface, and especially near electrodes. Practical applications are made in the determination: (1) of the continuity of a conducting orebody; (2) of the surface ares of an orebody; (3) in the detection of a water-bearing fault in a salt mine. Preliminary 'observations are described: (1) on the influence of the depth of ground-water table; (2) on the detection of gas under high pressure in coal seams. The observations in this paper of the electrical resistivity of rocks and soil in place are along the lines of the very interesting method and results of the Messrs. Gish, Rooney, Hotchkiss and Fisher. 1,2 All the work described has been done since 1920. Method Used The very simple method consists in the application to the rock of two plane circular electrodes of iron or brass of a suitable diameter, with the aid of a contact substance, and in measuring the resistivity in a Wheatstone bridge with alternating current of 100 to 400 Hertz frequency per sec.). The general formula is known to be R= R0 +d/4(1/a+1/b-1.7/l+0.8(a+b)/l2) (1)

Jan 1, 1929

By Strathmore R. B. Cooke, Iwao Iwasaki, Hyung Sup Choi

The effect of temperature as a parameter in ore flotation has not been systematically studied, although for some ores it has been known for many years that selectivity and grade of concentrates can be improved by conditioning or flotation at moderately or substantially elevated temperatures. In 1934 Coghill and Clemmer' stated that "elevated temperature seems to make hard water more tolerable" in soap flotation, and a cursory examination of the literature indicates that some earlier investigators were aware of beneficial results obtained by floating above room or mill-water temperatures. Tartaron,' Mitchell et al.,3 and particularly Hamilton et al." have shown that high pulp temperatures give high recovery and selectivity in soap flotation of fluorite from a variety of gangue minerals. As a result of the work of these and of other investigators, high-temperature flotation has been successfully applied to industrial flotation of fluorite. Falconer" stated: "The use of high temperature conditioning (above 35°C and preferably above 60°C) in connection with the soap flotation of nonsulphide ores, as covered in B. Kalinowski's French Patent No. 847,- 215, Dec. 7, 1938, is claimed to provide more intense activation, better separation of values from gangue, and reduction in quantity of reagents." The various investigations quoted above clearly demonstrate the improvements to be realized by increasing the temperature at which fluorite is floated, and it is surprising that little or no information has been published on systematic investigation of the same method as applied to other ores.

Jan 5, 1960

By John T. Wizzard, R. P. Killmeyer, B. S. Gottfried

The Coal Preparation Branch of the Pittsburgh Energy Technology Center has developed a computer program to calculate the performance characteristics of coal washing devices. This program uses specific gravity analyses of the clean coal and refuse streams as input, and generates dependent and independent performance criteria for the washer. Partition curves are internally represented in a functional form by a Weibull function. Performance criteria generated by this computer program are compared to manually calculated performance criteria for air tables, Dynawhirlpools, Baum jigs, hydrocyclones, and dense medium cyclones. The comparisons show that the computer program gives results in close agreement with the hand- calculated values while greatly reducing the amount of time involved in performing the analyses.

Jan 1, 1983

By D. Pearson

INTRODUCTION In 1975 278x10 3 tonnes of zinc was consumed in the United Kingdom, of which 69.3x10 3 tonnes was obtained from secondary sources. Of this secondary zinc 37.7x10 3 tonnes was used in brass making, the remainder was used in non metallic applications - eg oxides and salts. Many forms of zinc-bearing wastes arise, for example as galvaniser's drosses and residues, fumes from ferrous and non-ferrous metallurgical processes, and filter cakes from rayon manufacture and metal finishing. In the case of zinc-bearing dusts and fumes, the quantities available for recycle are at present restricted by the failure to collect them efficiently, hut environmental factors are leading to improvements in gas cleaning, with the result that quantities collected will increase and then exceed those required for the production of chemicals, so that some dusts may either have to be dumped or processed to metal. The recovery of zinc from steelmaking dusts is practised in W. Germany (1) and Japan (2) employing processes based on reduction in rotary kilns in order to produce sponge iron and a zinc- rich oxide suitable for feeding to the zinc-lead blast furnace. Although the zinc-lead blast furnace is the only zinc-making process used in the UK, no similar treatment of steelmaking dusts is carried out, a pilot scheme was tested by the British Steel Corporation, but development was abandoned for economic reasons. It appears to be cheaper to pelletise suitable dusts and export them for treatment elsewhere.

Jan 1, 1981

By W. J. Millard

VAGUE rumors and stories have been heard, from time to time, about the diamond and gold deposits of southern Venezuela. It is perhaps appropriate, at this time of revived interest in gold mining, to publish a few facts in regard to this country, which has been undergoing exploration since the fifteenth century. Gold and diamonds are found principally in the State of Bolivar which lies in southeastern Venezuela and is bounded by British Guiana on the east and Brazil on the south (see Fig. 1). The famous Mt. Roraima is situated at a point where these three countries meet in a common point (see Fig. 2). Some gold is also found in the southern part of the territory of Amacuro. Good oil prospects exist in the northern part of this same territory. Diamonds are found on the Caroni river from Rio Paragua to the village of Guri. Another small district is on the headwaters of the Cuyuni river. Quartz veins containing gold are chiefly exploited in

Jan 1, 1931

By J. F. Myers, F. M. Lewis

The paper reports the development of a large, slow speed ball mill closed circuited with a hydroscillator. This increased grinding efficiency 28 pct over conventional units.

Jan 1, 1950

By W. Rall, A. J. Birkle

The effect of fast-neutron irradiation on the micvo strcture of a common reactor pressure-vessel steel, A212 Grade B, was studied using thin-foil transmission electron microscopy. The dislocation density of the irradiated material is considerably greater than that of the nonirradiated control material. Annealing studies indicated that dislocations and hardness ill the irradiated material annealed out—as docs the radiation-induced embrittlement according to other- investigators— at temperatures STEELS in nuclear reactors are affected by neutron irradiation. In the American Society for Testing Materials (ASTM) A302B and A212B steels commonly specified by designers for reactor vessels, between 650° and 800°F. However, the dislocations and hardness in control samples cold-worked to 9 and 70 pct did not anneal out readily, and a high dis -location density was observed, even after a 1-hr anneal at 850°F. Based on the hypothesis that cllrster defects, rather than the increased dislocation density, are primarily responsible for mdicltiotz-iudziced e)nbriftlen7ent, reconzmendations are made for reducing the susceptibility to such ernbrittlement. exposures at a temperature of 550°F or lower to neutron dosages encountered during a 20- to 30-year life (-3 X 10'' nvt, >1 mev) may increase the nil-ductility transition temperature (NDT) as much as 300" or 400".'9 Therefore, to prevent brittle failures in reactor structures, extreme caution is required to reduce thermally induced stresses during all reactor shutdowns and startups when the temperature is below the NDT of the pressure vessel.

Jan 1, 1964

By Tuncel M. Yegulalp, Malcolm T. Wane

In general, many problems relating to the exploitation of mineral deposits are probabilistic in nature. This derives from the fact that the geologic universe is inherently random. Probability theory and statistics have been found useful for forecasting the behavior of natural events that occur in the geologic universe. The objective of this paper is to illustrate the application of the theory of extremes to this fore-casting problem. For example, it is customary for design purposes to determine the rupture strength of geologic materials. The theory of extremes is exceedingly useful in describing that portion of the frequency distribution of rupture strength which contains the least strengths. Parameters describing the distribution of the least strengths are more important to the designer of mining excavations than parameters describing the total distribution. The basic principles of the theory of extremes will be detailed and illustrated. Any person required to work in the laboratory of nature is aware that uncertainty is a salient feature of all mining enterprises. A mining engineer required to plan the most efficient, practicable, profitable, and safe mine finds himself face to face with numerous ill-understood and often unquantifiable states of nature. Basic information necessary for adequate planning is often lacking or derived from incomplete tests on samples or experience of doubtful validity. The planning procedure usually takes the form of determining a feasible layout with the intent of determining an optimal layout when and if the necessary details and information become available. The crux of the entire procedure is the choosing of numbers to put into the operational and structural models which encompass the plan. Many times these numbers must be assigned qualitatively from past experiences and are called the "most probable ones." At other times, load records, performance records and material tests provide a basis for extrapolation. In any event, the numbers are chosen from a distribution or set of all numbers. Since each number in the distribution represents a possible state, the choice of any particular value is based upon a decision rule. To illustrate, consider the design of an underground structure or the design of a rock slope. The initial step is the formulation of the various possible structural actions which result from the geometry of the layout. For a given structural model various intensities of behavior are possible depending upon the load, deformation, and material characteristic spec-trums, respectively. Of particular interest to mining people is the failure behavior or condition, i.e., when there is a complete collapse of structural resistance by either structural instability or fracture. A necessary feature of the analysis is the "rupture strength" of the material. Information on the rupture strength is derived from testing either in situ or in the laboratory and the usual outcome is a variation in the test results. The methodology used to overcome this variation is to construct a frequency distribution of rupture strengths, and then determine a measure of central tendency and variability. The main idea involved is that the central tendency number will be used in the failure calculations and the measure of dispersion will be used to estimate the probability of failure. In particular if the distribution of rupture strength is normal, the mean rupture strength is the central tendency number and the standard deviation of the rupture strength is the measure of variability. Suppose the mean value of rupture strength is 1000 psi and the standard deviation is 200 psi. Insertion of 1000 psi into the failure calculation produces results that are unsafe, hence a common decision rule is to reduce the mean value by a "factor of ignorance" so that the failure calculation will produce a "safe result." If two is chosen as a factor of ignorance, this means the value inserted in the calculation is 500 psi or 2.5 times the standard deviation. The next step is to determine the percentage chance that failure will occur from a design created on this basis. Tables on the normal distribution function show that this percentage chance is 0.621% or approximately 7 times out of 1000. In practice, however, the situation is more complicated than represented by the foregoing illustration. The laboratory or field testing program usually constitutes a pathetically small sample of the geologic universe of interest and not enough testing is carried out to determine the exact form of the distribution of the test results. The normal, Cauchy and Student's T distributions are strikingly similar, and it becomes a matter of mathematical convenience to assume the normal law for phenomena which follow other laws.

Jan 1, 1969

By d&apos, K. Mukherjee, C. R. Antonio, R. J. Maciag, G. J. Fischer

Tensile data indicate that over the range of strain rates 10-5 to 10-1 sec-1 and in the temperature range 298° to 743°K the flow stress at a given temperature may be expressed as: C0 = Cem where m changes abruptly at a critical strain rate of 10-2 sec-1. The Zener-Hollomon parameter was tested and found to be invalid except at temperatures exceeding 700° K. Values of AH calculated for temperatures above 700°K ranged from 30 to 47.5 kcal per g-mole. ThE flow characteristics of aluminum and aluminum alloys as a function of temperature and strain rate have been of interest to various experimenters for many years. Trozera et al.1 determined tensile flow curves for pure aluminum and concluded that the combined effect of temperature and strain rate on the flow stress could be related using the Zener-Hollomon parameter. More recently, Hockett2 proposed a relationship between compressive flow stress, temperature, and true strain rate which could be represented by a surface. Holt et al.3 studied strain rate effects on flow stress in a number of aluminum alloys at room temperature. It was determined that there is a critical strain rate above which a strain rate effect is observed. It was also reported that the strain rate sensitivity was significant in aluminum alloys in the "0" condition only. In a recent review paper McQueen4 has considered a number of mathematical expressions which have been used to describe the relationship between stress, strain rate, and temperature. These expressions have been applied to the flow characteristics of a number of different metals and alloys including aluminum. In the present work the strain rate sensitivity of 7075-0 aluminum was determined in the temperature range of 298° to 743°K. The tensile flow stress at 0.2 pct offset was obtained over a nominal strain rate range of 10-5 to 10-1 sec-1. EXPERIMENTAL Threaded tensile specimens were cut from a single heat of 7075-T6 aluminum. The composition of this heat is given in Table I. The test bars had a gage section 1.5 in. long by 0.250 in. diam and conformed to ASTM specification E-8-57T. After machining, the bars were annealed at 413° ± 10°C for 2 hr. They were then cooled to 260°C in 3 hr, and finally air cooled to room temperature. This treatment is commonly used to produce the "0" condition. Load-time curves at constant crosshead speeds were obtained at various temperatures using an Instron testing machine. Crosshead speeds ranged from 0.002 to 40 in. per min. A three-zone resistance tube furnace was used for the elevated-temperature tests. Temperatures were measured at three points along the gage length by means of suitably placed thermocouples. Each tensile bar was held at temperature for 30 min prior to testing and the maximum temperature variation along the gage length was kept below 1°C. In all, 275 samples were tested and each data point plotted is an average of at least two tests. In many cases the point represents up to six tests. RESULTS AND DISCUSSION Values of the flow stress at 0.2 pct offset at six different temperatures are plotted vs strain rate on log-log coordinates in Fig. 1. Over discrete ranges of strain rate, the data for each temperature fit the expression:

Jan 1, 1969

By A. T. Sweet, C. E. Plummer, H. W. St. Clair, S. F. Ravitz

The ammonium sulphate process for recovering alumina from clays was proposed by Rinman, Buchner, and others many years ago, and more recently various modifications have been investigated both here arid abroad.l-Is The process, as it is being investigated by the Bureau of Mines, involves the following essential steps: (I) sulphating the alumina in the clay by baking with ammonium sulphate at approximately 4m°C., (2) leaching with water to extract aluminum sulphate and ammonium sulphate, (3) crystallization of ammonium alum, (4) conversion of the alum to aluminum hydroxide by the ammonia gases given off during the baking, and (5) calcining the aluminum hydroxide to alumina. The over-all reaction between kaolinite (the most important alumina mineral in most clays) and ammonium sulphate during the baking step may be expressed as follows: Al2O8.2SiO2.2H2O + 4(NH4)2SO4 = (NH4)2SO4.A12(SO4)3 + 6NH3(g) + SH2O(g) + 2SiO2 [i] There is definite evidence. as is shown later. that the aluminum occurs in the baked product as anhydrous ammonium alum rather than as aluminum sulphate, provided the baking temperature is not much above 4o0°C. It is probable that the reaction takes place in the following steps: (NH4)2SO4 = NH3 -(- NH4HSO4 [2] Al2O3.2SiO2.2H2O + ;}NH4HSO4 = A12(SO4)3 + 3NH3 + 5H2O + 2SiO2 [3] A12(SO4)3 + (NH4)2SO4 = (NH4)2SO4.A12(SO4)3 [4] In onc modification of the process, the ammonium sulphate is first decomposed according to Eq. z, and the clay is treated with the resultant ammonium acid sulphate. Reaction I is highly endothermic. On the basis of the best available data, the following values have been estimated for the changes in heat content and free energy in calories per mol: -AH = 331,040 - 34T -AF = 331~040 - 78.3T log T - 671.8T The heat required' at 25OC is 320,900 cal. per mol, or 5650 B.t.u. per pound of alumina. The theoretical equilibcium pressure of NHa, based on the free-energy equation given above, increases very rapidly as the temperature rises above 3o0°C., and reaches one atmosphere at 43s°C. Ammonium alum solutions are almost ideal for crystallization. A saturated solution of ammonium alum contains 126. grams of AlzOa per 1000 grams of water at 90°C. and only 16.5 at 20 C. Hence most of the alum crystallizes out when the

Jan 1, 1944

By R. J. Hopkins, L. B. Haney

On the basis of limited experimental work conducted at the Port Pirie smelter, it would appear that, by increasing the specific surface of sinter, and possibly that of coke as well, a marked increase in the rate and degree of sinter reduction in the furnace shaft can be achieved. Fusion-point tests have shown that this increased reduction means a much higher sinter fusion point and narrower plastic zone, while the more efficient utilization of coke in the furnace is inherent in the intensification of reduction by the provision of a more reactive sinter surface. Investigations aimed at increasing the ability to operate the blast furnace with a higher lead tenor of sinter reducing fuel cost proportionately, and at eliminating the loss in reduction potential in coke entering the furnace, as shown by the presence of appreciable proportions of CO in the top gases, are reported. Several lines for future investigations that could result in improved smelting methods are proposed. A SOMEWHAT informal presentation of ideas on lead blast-furnace smelting will be given in this paper. These ideas have been developed during observations of furnace behavior at Port Pirie and earlier at Mt. Isa, and have been guided by the results of laboratory experiments at Port Pirie. The authors do not intend to propound any particularly new theories, but present their ideas as a basis for discussion which may help toward a better understanding and improved control of blast-furnace operation. Performance variations of considerable magnitude occur from time to time at most lead blast-furnace plants. While Port Pirie is fortunate in having a very regular supply of high grade concentrates, it is no exception in this respect. Such irregularities are of considerable economic importance and they constitute a challenge to present-day metallurgists in their efforts to obtain an ever greater degree of control over furnace operation. In operating as Port Pirie does with a relatively high lead charge, it has been recognized for a long time that shaft conditions are ,of the greatest importance. A practical, or engineering, attack on the problem of accretions consisted of changes in furnace design, e.g., by widening the shaft to 10 ft above the bottom row of tuyeres, and by the provision of curved ends and vertical walls.' That this attack has had a great measure of success is shown by the fact that barring down of these wide furnaces is rarely necessary, shaft conditions have greatly improved, and sensitivity to charge variations has been markedly reduced. These modifications, followed by some metallurgical changes (chiefly the incorporation of pig iron into the furnace charge in 1948), have brought furnace operation to a point where some variables which were previously masked can now be studied. Accordingly, over different periods of time during the last five years, such variables as could be given numerical values have been recorded and subjected to statistical examination. The objectives of this work were: 1—to reveal the true importance of the different variables and 2—to show the proportion of total furnace variation which is unexplained and therefore referable to causes not measured at present? e.g., shaft accretions, sinter structure, coke structure, and others. Statistical Study of Variables In this work factors relating to furnace speed and lead reduction have been examined: 1—slag com-

Jan 1, 1955

By M. J. GAVEN

COMING over from the plant on the Denver and Rio Grande yesterday afternoon I was an interested listener to a smoking-room conversation that had to do with the experimental plant near Rifle. The people who were talking didn't know me and I didn't know them, but I learned quite a little. I understood that the plant would never operate; that it was not intended to operate; that the "oil trust" would keep it from operating; that our tramway had eaten up all our money and still was not working and would not work; that the plant was run by a bunch of kids, and that the superintendent was probably the biggest kid of the bunch. I plead guilty to the latter. But the people who were talking were misinformed. The plant is producing oil. The first sample of oil that came from our unit at the Bureau of Mines experimental plant at Rifle, Colo., was produced on Sept. 18, the first that came out of the condenser, and it is still coming. This sample of oil may mean to the United States what the first oil produced from the first well meant.

Jan 1, 1926

H. Van F. Furman, Denver, Colo. (communication to the Secretary): There are some statements in Dr. Carpenter's interesting paper which appear to require explanation, if not modification.

Jan 1, 1901

By R. Haynes

ON the basis of compositional changes of a phase observed in a eutectoid Cu-Al alloy1 it has been suggested that mechanisms for the decomposition of the ß phase proposed by earlier workers2-5 were incorrect. These data are reinterpreted in conjunction with lattice parameter data obtained on an alloy containing 12.2 pet Al, whose isothermal transformations have been reported elsewhere.5 The a Lattice Parameters of a 12.2 Pet A1-Cu Alloy—~iffraction patterns of completely transformed specimens were obtained in a back reflection camera using copper Ka radiation. Lattice parameters of

Jan 1, 1959

By J. B. Newsom

IN the September 1936 issue of MINING AND METALLURGY the pioneer work of boring a 5-ft. shaft to a depth of 1125 ft. at the Idaho Maryland mine in California was described. Later, a Bureau of Mines Information Circular (No. 6923) gave additional data. In re¬cent months still further progress has been made in this technique through the sinking of a 5 1/2-ft. shaft for Pickands, Mather & Co. at their Zenith mine, Ely, Minn. The present work was done with new carefully designed equipment and several experienced men so that progress, as shown below has been much better:

Jan 1, 1938

By Edward Keller

(New York meeting, February, 1912.) IN a paper, entitled A Uniform Method for the Assay of Copper Material for Gold and Silver,1 A. R. Ledoux invited the assayers of this country to contribute to a symposium, in which the results of their assays of given samples of copper-matte and metallic copper would be made comparable. This symposium 2 appeared about one year thereafter; and through it and its discussion, first became generally known the fact that the ,gold-yield by the all-fire method of assaying is usually higher than by the so-called combination (wet and dry) method, in which nitric acid is employed as a solvent for the copper. In the publication alluded to, the supposed cause of gold-losses in the latter method was declared to be the solvent action of copper nitrate, or of the reduction-products of the nitric acid, upon the gold. Up to a very recent date, gold has been held to be insoluble in pure nitric acid. (The solvent action of any chlorine present in the nitric acid must here properly be disregarded as belonging in the realm of carelessness. Among later allusions to this topic, W. R. Tan Liew 3 ascribes the solution of the gold in the combination-assay entirely to the action of nitrous acid at the high reaction-temperature of copper and nitric acid ; F. B. Flinn 4 a believes the low result in gold to be due exclusively to mechanical losses-finely-divided gold penetrating through the filter-paper-but presents no experimental data confirmative of this belief; and 0. Pufahl 5 attributes the solubility of the gold in some coppers to the presence of selenium-a view which appears to be shared by many as- 1 Trans., xxiv., 575 (1894). 2 Trans., xxv., 250 (1895). 3 Engineering and Mining Journal, vol. lxix., No. 16, p. 469 (Apr. 21, 1900). 4 Engineering and Mining Journal, vol. lxxxvii., No.11, p. 569 (Mar. 13, 1909). 5 Lunge, Chemische Technische Untersuchungs Methoden, vol. ii., p. 229 (1900).

Jul 1, 1912

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-' cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964