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By R. W. Stormont, F. Wald

The phase diagram of the Pseudobinary section PbTe-Fe was determined. It was found to contain a monotectic and a eutectic reaction, the latter one taking place at 14 at. pct Fe and 875° * 5°C. The solid solubility of iron in PbTe was found to be 0.3 at. pct by electronmicroProbe analysis. No solubility of PbTe was detected in iron. Slight deviations from true pseudobinary behavior were found to occur in the range of - 5 to 10 at. pct Fe. In the course of a general investigation of reactions of various metals with lead and tin telluride,' the lead telluride-iron system was reinvestigated. It had been established much earlier than iron does not chemically react with lead telluride but forms a eutectic with a melting point of 879" The eutectic composition or other related information has never been reported, but for a number of years iron has been in general use for contacting of lead telluride and lead telluride alloys for thermoelectric applications. It seems therefore desirable to clarify the exact constitution of the system to furnish a base for the long-term evaluation of bonds made between lead telluride and iron either by pressure contacting or by brazing methods. I) EXPERIMENTAL METHODS Lead telluride-iron alloys were prepared in 10-g charges, using premelted lead telluride. This material was prepared from high-purity, semiconductor-grade lead and tellurium obtained from the American Smelting and Refining Co. and described as 99.999 pct pure. The iron used was "Armco" iron; the major impurities found here were 0.02 pct C, 0.018 pct Si, and 0.015 pct Cr. All remaining impurities were less than 0.01, the total of all impurities not exceeding 0.15 pct. Charges were prepared in closed quartz arnpoules which were evacuated and in some cases backfilled with high-purity argon to retard excessive lead telluride evaporation and deposition in slightly cooler parts of the ampoule. For high iron concentrations, this can lead to total separation of the constituents, since the vapor pressure and the sublimation rate of PbTe are quite high.4 Nevertheless, since the ampoules are closed, no change in overall composition was expected and the nominal composition of all alloys was assumed to be retained. X-ray diffraction analysis, thermal analysis, and microsections were used in the evaluation of the alloys. The nature of the system was such that X-ray diffraction was not particularly helpful. It merely served to establish that at all concentrations PbTe and a! iron were in equilibrium at room temperature. Thermal analysis was carried out by taking direct temperature vs time curves on a Sargent recorder where a width of 10 in. was kept as 1 or 0.5 mv by use of an automatic bucking voltage network. Quartz ampoules with minimized dead space, coated with boron nitride and fitted with a thermocouple reentrant, were used as containers for the charge. At high temperatures and over long periods of time, boron nitride reacts with iron. For the thermal analysis runs, however, this was not significant. More significant was the fact that the vapor pressure of PbTe at some of the meas -uring temperatures apparently exceeded I atrn quite considerably. This, in some cases, caused the slightly softened quartz tubes to blow out if great care was not taken to contain them and minimize time and temperatures used. As containers pure nickel tubes were used which also served to avoid temperature gradients in the quartz ampoule. Nevertheless, the experimental difficulties at high temperatures were severe and the monotectic temperature could therefore not be determined accurately. In general, the accuracy reached by the thermal analysis setup in this case is *4"C as determined with gold, silver, and tin, under the conditions of analysis here. Inherently, the apparatus is capable of reaching accuracies better than i 1°C. Also, difficulties were encountered in microsection-ing. They were related to polishing, since it is rather difficult to avoid pulling the iron out of the weak and brittle lead telluride matrix. It proved best to follow a procedure where, after grinding to 600 grit on carborundum paper, a polish with 6 p diamond was used on nylon cloth. Finally, #3 "Buehler" alumina and an automatic polisher were used for -5 min only, to avoid relief. The best etching results were achieved with

Jan 1, 1969

By R. H. Oliver

The purposes, types, preparation, and testing of flocculants are discussed. A flocculation compendium is included, indicating choice of flocculant for a given set of conditions. An economic evaluation of the process is presented. Solid-liquid separation is a major expense in most mineral processing flowsheets today. Proper use of flocculation can often lower the overall cost of a solid-liquid separation by reducing the size of sedimentation or filtration equipment. PURPOSE OF FLOCCULATION When is use of a flocculant justified in terms of overall process economy? 1) when it results in process improvement, such as producing a clear liquor for electrolysis, precipitation, ion exchange, or solvent extraction; 2) when it results in satisfying requirements of pollution abatement ordinances; 3) when it results in increased recovery of values that would otherwise be lost; or 4) when it results in considerable savings in capital expenditure due to use of smaller equipment. When can the use of a flocculant adversely effect overall process economy? 1) when it results in increased filter cake moisture, 2) when it results in decreased filtration rates, 3) when it results in considerable bulking of sedimentation underflow, 4) when it contaminates either the supernatant or sludge, or 5) when the cost of using the flocculant is greater than the savings due to its use. First step in consideration of flocculants for a given application is establishment of desired goals in terms of increased clarity of effluent, increased recovery of solids, or decreased size of equipment. The most economical solution to a solid-liquid separation problem is that combination of equipment and flocculant costs which meets the established goals at the lowest total annual expenditure. This economic decision can be made only after technical data has been obtained as outlined in next four sections. TYPES OF FLOCCULATION Flocculation is a process wherein individual particles are united into more or less tightly bound agglomerates or flocs, thereby increasing effective particle size of solids suspended in a liquid. Degree of flocculation of a suspension of finely divided solids in a liquid is controlled by a combination of probability of collision between particles and probability of adhesion after the collision has occurred.' Probability of collision can be increased commercially through use of a paddle-type flocculator, combination flocculator, and clarifier or flocculating-type feedwell. Probability of adhesion usually can be increased by addition of a reagent known as a flocculant. Reagents act as flocculants through one or a combination of three possible mechanisms. The first is electrolytic neutralization of inter molecular repulsive force due to Zeta potential. This neutralization enables Van der Waal's cohesive force to hold the particles together after they collide.' The second is the precipitation, within a definite pH range, of voluminous metallic hydroxide flocs which entrap fine particles. This process is known as coagulation.14 Third is the bridging of two or more particles by either natural or synthetic long-chain, high-molecular-weight organic polymers. This bridging is accomplished by adsorption of two particles at different sites on the same molecule or by bonding of two molecules, each adsorbed to a different particle. Considerable effort has been expended in explaining the action of these polyelec-trolytes and detailed accounts are available in the literature. CHOICE OF FLOCCULANTS It is impossible, at the present time, to specify the optimum type or amount of flocculant for a given application from a knowledge of the material to be treated. The standard procedure is to choose reagents or combination of reagents most likely to be effective on the slurry; then test them.' The accompanying Flocculation Compendium (Table I) contains details of all currently available reagents sold as flocculants and it should be used when selecting the group of reagents for tests. This selection can be based on information listed in columns 4 and 5. Column 4 presents industries in which each floc-

Jan 1, 1961

By Sylvan Cromer

The need for a clear understanding of the physical nature of the flow of gas-liquid mixtures in vertical pipes is ever becoming more apparent. This type of flow is encountered when gas and oil are produced from a well; when water is removed from gas wells with siphon lines and when liquids are elevated by means of air or gas lift. Although a number of investigator1-7 have published data on the flow of gas-liquid mixtures, in only a few cases has the experimental setup been devised to permit visual study. In the fields of heat transmission, such as the boiling of liquids and the study of the critical phenomena of the hydrocarbons, researchers have been able to throw additional light on heretofore unexplainable happenings through actual observation in glass apparatus. This investigation was therefore undertaken in order to obtain qualitative as well as quantitative results for air-water flow. Experimental Apparatus and Procedure The flow column used in these tests was made of standard 2-in. pipe and was approximately 98 ft. in height. Pyrex observation sections 2 ft. long having the same internal diameter as the wrought-iron pipe were placed at 14-ft. intervals in the column. The bottom of the tube was cut off square and terminated in the mixing chamber. No perforated nipple or footpiece of any kind was used. To the top of the column was fastened a semicircular return bend having a 4-ft. radius. The flow column was supported by a standard cable-tool drilling derrick (Fig. 1) into which were built observation platforms at each Pyrex section.

Jan 1, 1940

By Sylvan Cromer

The need for a clear understanding of the physical nature of the flow of gas-liquid mixtures in vertical pipes is ever becoming more apparent. This type of flow is encountered when gas and oil are produced from a well; when water is removed from gas wells with siphon lines and when liquids are elevated by means of air or gas lift. Although a number of investigator1-7 have published data on the flow of gas-liquid mixtures, in only a few cases has the experimental setup been devised to permit visual study. In the fields of heat transmission, such as the boiling of liquids and the study of the critical phenomena of the hydrocarbons, researchers have been able to throw additional light on heretofore unexplainable happenings through actual observation in glass apparatus. This investigation was therefore undertaken in order to obtain qualitative as well as quantitative results for air-water flow. Experimental Apparatus and Procedure The flow column used in these tests was made of standard 2-in. pipe and was approximately 98 ft. in height. Pyrex observation sections 2 ft. long having the same internal diameter as the wrought-iron pipe were placed at 14-ft. intervals in the column. The bottom of the tube was cut off square and terminated in the mixing chamber. No perforated nipple or footpiece of any kind was used. To the top of the column was fastened a semicircular return bend having a 4-ft. radius. The flow column was supported by a standard cable-tool drilling derrick (Fig. 1) into which were built observation platforms at each Pyrex section.

Jan 1, 1940

By A. H. Geisler, J. H. Keeler

Preferred orientations in rolled and annealed titanium sheets were determined by the Geiger counter spectrometer X-ray diffraction technique. Five annealing textures dependent upon the temperature range of annealing were found, and in order of increasing annealing temperature pendent upon the temperature range are: 1—a deformation like texture, 2—a rotated inorder a-recrystallization temperature texture, 3-a retained u-recrysraIlization texture, on annealing at lower temperatures of the ß-region, 4—a transformation texture based on recrystallized a and predicted by the Burgers' relationship, and 5—a ,ß-cube texture. These results are examined in terms of current theories of recrystallization textures. UMEROUS investigators have described the tex- ture obtained by cold rolling the hexagonal metals, titanium, zirconium, and beryllium, which have c/a ratios less than that of ideal packing, 1.633. The basal planes are rotated out of the rolling plane, about the rolling direction, so that the basal poles are tilted toward the transverse direction as shown schematically in Fig. la. In all instances but one,' it was also reported that the [1010] direction was parallel to the rolling direction (see Fig. lb). Hot rolling has been reported as causing a similar tilt of the basal poles in the transverse direction (see Fig. la) and causing the [1010] direction also to be parallel to the rolling direction as shown schematically in Fig. lb. Annealing after deformation does not appreciably change the tilt of the basal poles in the transverse direction." Beryllium2-7 continues to have the [1010] direction in the rolling direction after annealing, and similar observations for titanium and zirconium' . have been reported for annealing at fairly low temperatures, again as in Fig. lb. At higher annealing temperatures, however, the recrystallized grains of titanium" and zirconium have an orientation such that the [1120] direction is approximately in the rolling direction, although the basal poles are still inclined in the transverse direction. Figs. la and lc show the resulting orientations schematically. This change in orientation has been described as a nominally ±30° rotation of the hexagonal crystallites about the basal poles of the cold rolled texture and is apparent from the results which are summarized in Table I for investigations with the X-ray diffraction technique employing film. The angles y, , and ß are indicated in Fig. 2 which represents the stereographic projection of (1070) poles for the mean orientation of a pole figure. Texture determinations for titanium using the Geiger counter spectrometer have provided similar results except that in some instances additional components of the texture were proposed, as shown by the summary of data in the upper half of Table 11. On the other hand, the spectrometer technique, when applied to zirconium,* has revealed a splitting Recently completed studies of the textures of annealed zirconium", show zirconium to possess textures very similar to those reported here for titanium. Therefore, much of this discussion will include zirconium by virtue of its close similarity to titanium in pref erred orientations. of the intense areas of the pole figure for samples annealed at 600°C. This splitting could be described by a 7" rotation of the tilt axis about the normal to the rolling plane. Such a splitting for the annealed texture relative to the cold rolled texture was not observed in other determinations for either zirconium or titanium using the less sensitive film X-ray methoe and makes the relationship between the two types of texture more complex than the simple rotation about the (0001) pole based on film work. The more precise investigations on zirconium permit the descriptions in the lower part of Table 11, which show that the texture depends quantitatively on the temperature of annealing. When zirconium is annealed at temperatures up to 400°C, the texture is similar to the cold rolled texture, while annealing in the range 500" to 900°C produces a texture which is only approximately described as [11%] in the rolling direction. More precisely described results for zirconium show that the two types of splitting ( 1—about an axis in the rolling plane through an angle given in the second column in Table II and 2—about the normal to the rolling plane through an angle given in the third column of Table 11) depend on annealing temperature. The [1120 is the rolling direction only when the annealing temperature is in the vicinity of 900°C

Jan 1, 1957

By Schumacher, Earle E.

THE solidus line above the solid solution field in the lead-antimony system was originally determined by Dean and his associates1 from heating curves. They did not regard this line as having been accurately fixed and in their more recent publications2 the curves drawn do not follow closely the original data. The precise location of the solidus line is of importance in the extrusion of lead-antimony cable sheath, as the temperature of the metal in this process must be less than the lowest temperature at which any part of the alloy in the lead-press charge becomes liquid. It is very desirable, however, to operate at as high a temperature as possible, as the rate of extrusion for a given pressure is approximately doubled for an increase of 10" C. in temperature. The precise location of this line is also important in the investigation of ternary systems of lead, antimony and a third metal. For these reasons, and because of the differences reported in the literature, data were secured on the lead-antimony solidus line by the classical quenching-test procedure.

Jan 1, 1927

By A. M. Turkalo

IT is a well-known fact that martensitic steels show a greater resistance to brittle fracture than do pearlitic and bainitic steels. It was, therefore, thought worthwhile to investigate the mode of brittle fracture with respect to structure by studying the effect of various austenite decomposition products on the propagation of brittle fracture in steel by means of electron microscopy. Newly developed replication techniques together with the advantages of the electron microscope such as great depth of field, available high magnification and easy adaptation to stereophotography make electron microscopy very suitable for fracture studies. EXPERIMENTAL PROCEDURE An essentially plain carbon steel containing 0.56 pct C, 1.30 pct Mn, 0.02 pct P, 0.03 pct S and 0.22 pct Si was used in this investigation. The following table gives the heat treatments used to obtain the various austenite decomposition products: The resulting austenite grain size from the 870°C austenitization treatment was about an ASTM No. 7 grain size. The specimens which were 2 in. long, 1/4-in. diam bars were austenitized in a tube furnace through which argon gas was blown. The tube was not, however, air-free and the specimens were not completely oxide-free. Isothermal treatments were done in a lead bath. With the exception of the fully hardened specimen and the one as-isothermally transformed at 300°C the heat treated specimens were notched in the following fashion with a jeweler's saw. A cut about 0.08 in. deep was made perpendicular to the length of the bar. The specimen then was rotated about 45 deg and another cut about 0.08 in. deep was made. In the case of the hard martensitic and bainitic specimens, only one cut was made and the depth was not controlled. The design of the two-cut notch caused fracture to initiate at the point of intersection of the two saw cuts. The specimens were broken at -196°C in a Charpy impact testing machine. In order to hold the specimens securely in the impact machine two square pieces of mild steel were made about 5/8 in. long having the same cross section as that of a standard Charpy specimen but containing a hole 1/4 in. diam through the center of the cross-section. These adapters were slipped over the ends of the test specimen which was then secured tightly by means of set screws in the adapters. The specimen with the adapters was cooled to -196°C in liquid N,, then placed in the impact machine and broken within 3 sec. One half of the broken specimen was used for the electron microscope study of the actual fracture surface. The other half was nickel-plated and a cross section through the notch and fracture was polished for electron microscope examination. Carbon replicas of the fracture specimens for the electron microscope study were made essentially according to Bradley's evaporation technique.' Both direct carbon and two-stage carbon replication techniques were used. In the case of the direct carbon technique, a thin layer of carbon was evaporated first at an angle of about 45 deg to the mean fracture surface and then another film of carbon was evaporated normally to the fracture surface. The carbon replica was freed electrolytically.2 The specimen was made an anode in a 10 pct Nital polishing solution. It was etched intermittently by shutting off the power now and then. The freed replica was washed in 40 to 50 pct water solution of nitric acid for 10 min or so, then washed in water and picked up on a screen for examination. The two-stage carbon replication technique involved first making a primary replica of cellulose * acetate from which a carbon replica was then made. One side of a strip of cellulose acetate wet with acetone was pressed lightly against the surface of the specimen, allowed to dry and then stripped. Prior to the deposition of carbon, which was done at 90 deg to the cellulose acetate replica surface, chromium was evaporated at 45 deg. After the carbon evaporation the cellulose acetate was dissolved in acetone according to the Jaffe method3 leaving the carbon replica preshadowed with chromium for examination.

Jan 1, 1961

By H. W. McCue

In 1945 the number of oil wells drilled was less than in 1944 but the number of gas wells was greater. The oil wells numbered 176, completed for an initial production of 25,214 bbl., an average of 143 bbl. per well as against a total in 1944 of 245 drilled for 32,886 bbl., or 134 bbl. per well. All of these wells were in proven areas and no new discoveries

Jan 1, 1946

By J. F. K. Brown, E. E. Roecker

For three years The Hudson Coal Co. has used egg anthracite instead of coke in its foundry cupola. It has long passed the stage of being told it cannot be done—the metal would be cold, of poor quality, or the speed of operation would be low. From observation, from use and from test. we know that our metal is about average; the cast iron invokes no adverse comment from the machine shop and the speed suits our foundry requirements. We have there-iore resolved into practice anthracite combustion processes in an industrial furnace formerly using coke, under conditions suitable to our needs. When it comes to translating what we know into use in another cupola, however, where operating conditions may be different, or to explaining why, with seemingly the same conditions in our own cupola, we have attained sometimes a temperature of 2800° in the metal and at another time 2600°, or a speed of 5 tons per hour against 2 35 tons per hour, we cannot do it. We cannot do this because there seems to be an unbridged gap between laboratory ideas on combustion and practical ideas on com-bustiqn, which we have been unable to cross in terms understandable to us as practical consumers. This gap or bridge centers around the problem of how combustion actually takes place; and we believe it is controlled by two factors: (I) the character of the surface of the fuel and (2) the space provided and needed within which the oxygen of the air is allowed to or can act on that surface. It has long been contended on behalf of coke that porosity is an important factor in combustion, although, admittedly, there are two schools of opposing thought on this question, as revealed in technical literature. It has been understood generally that a light, porous coke is the best metallurgical fuel because there are more square inches of carbon exposed to the blast of air, therefore more useful carbon-dioxide reactions can take place in the given space between the entrance of the air and the point where useful work is done. It is now our general idea that the heavier and the harder the coal, the better the metallurgical fuel, provided the surface of that fuel is suitable for fast reaction with the oxygen. Time and Space A cupola is loaded in layers of fuel and iron. The horizontal line where the first charge of iron rests on the coal is the top of the bed coal. With us that is 22 in., usually, above the tuyeres where the air enters. This means 600 lb. of coal. Every subsequent coal layer is 100 to 125 lb. of coal, and that 100 to 125 lb. of coal melts 1000 lb. of iron at around 2700° in the ladle. This quantity of coal represents a 3-in. layer spread across the cupola. The question arises: If this 3 in. of coal will melt 1000 lb. of metal, why was it necessary to use 600 lb., or 22 in., of coal beneath and between the first charge of iron and the air entrance?

Jan 1, 1944

By E. E. Roecker, J. F. K. Brown

For three years The Hudson Coal Co. has used egg anthracite instead of coke in its foundry cupola. It has long passed the stage of being told it cannot be done—the metal would be cold, of poor quality, or the speed of operation would be low. From observation, from use and from test. we know that our metal is about average; the cast iron invokes no adverse comment from the machine shop and the speed suits our foundry requirements. We have there-iore resolved into practice anthracite combustion processes in an industrial furnace formerly using coke, under conditions suitable to our needs. When it comes to translating what we know into use in another cupola, however, where operating conditions may be different, or to explaining why, with seemingly the same conditions in our own cupola, we have attained sometimes a temperature of 2800° in the metal and at another time 2600°, or a speed of 5 tons per hour against 2 35 tons per hour, we cannot do it. We cannot do this because there seems to be an unbridged gap between laboratory ideas on combustion and practical ideas on com-bustiqn, which we have been unable to cross in terms understandable to us as practical consumers. This gap or bridge centers around the problem of how combustion actually takes place; and we believe it is controlled by two factors: (I) the character of the surface of the fuel and (2) the space provided and needed within which the oxygen of the air is allowed to or can act on that surface. It has long been contended on behalf of coke that porosity is an important factor in combustion, although, admittedly, there are two schools of opposing thought on this question, as revealed in technical literature. It has been understood generally that a light, porous coke is the best metallurgical fuel because there are more square inches of carbon exposed to the blast of air, therefore more useful carbon-dioxide reactions can take place in the given space between the entrance of the air and the point where useful work is done. It is now our general idea that the heavier and the harder the coal, the better the metallurgical fuel, provided the surface of that fuel is suitable for fast reaction with the oxygen. Time and Space A cupola is loaded in layers of fuel and iron. The horizontal line where the first charge of iron rests on the coal is the top of the bed coal. With us that is 22 in., usually, above the tuyeres where the air enters. This means 600 lb. of coal. Every subsequent coal layer is 100 to 125 lb. of coal, and that 100 to 125 lb. of coal melts 1000 lb. of iron at around 2700° in the ladle. This quantity of coal represents a 3-in. layer spread across the cupola. The question arises: If this 3 in. of coal will melt 1000 lb. of metal, why was it necessary to use 600 lb., or 22 in., of coal beneath and between the first charge of iron and the air entrance?

Jan 1, 1944

By A. E. Nehrenberg

IN an earlier publication' it was shown that the.. shape assumed by a volume of growing austenite is inherited from the prior structure. The matrix grains of pearlitic microstructures are equiaxed, and austenite grows in an equiaxed manner in these prior structures. Martensite and bainite, on the other hand, have an acicular grain structure, and the austenite produced in such structures grows in an acicular manner. In the discussion of this paper' it was pointed out that in cold-rolled tempered martensite, austenite grows in an equiaxed, rather than an acicular manner. The results of an experiment carried out to arrive at an understanding of this behavior are illustrated by the micrographs. Fig. 1 shows the acicular microstructure produced by heating tempered martensite to a temperature within the Ac1-Ac3 range, 1350°F. When tempered martensite is cold rolled, then heated to the same temperature, the equiaxed structure shown in Fig. 2 is produced. A sample of cold-rolled tempered martensite heated at 1350°F just long enough for the formation of a small amount of austenite is shown by Fig. 3 to have an equiaxed (recrystallized) ferrite grain structure. The small particles of. austenite which formed at 1350°F in the equiaxed ferrite matrix are likewise equiaxed. Thus, the equiaxed growth of austenite in cold-worked tempered martensite is not a contradiction of the principles described in the previous paper, for the growth pattern reflects the matrix grain structure existing at the time of austenite formation. References A. E. Nehrenberg: The Growth of Austenite as Related to Prior structure. Trans. AIME (1950) 188, pp. 162-174; Journal of Metals (January 1950). 2 J. R. Vilella and R. A. Grange: Discussion of ref. 1. Trans. AIME (1950) 188, pp. 1378-1381; Journal of Metals (November 1950).

Jan 1, 1953

By E. V. Potter, H. C. Lukens

THE volume of hydrogen released from electrolytic manganese at various temperatures and pressures was determined in a previous investigation1 as part of a study to determine the most practical procedure for removing the hydrogen from electrolytic manganese metal. No attempt was made to determine the absolute volume of gas in the metal at any temperature and pressure; the volume of gas released showed only the variation in solubility with temperature and pressure. The results were very similar to those obtained by Sieverts and Moritz.2 Both sets of data show a minimum solubility between 500° and 700°C., but they differ in certain respects; on cooling from 500°C., our results showed an increase in solubility of about 7 C.C. as compared with an increase of 34 C.C. per 100 grams shown by Sieverts. Furthermore, the transition temperatures, as indicated by sharp breaks in the solubility curves, did not agree well with Sieverts' data. This information was of secondary importance in the earlier investigations, and the solubility at low temperatures and the transition temperatures were subject to considerable error. There- fore, a subsequent investigation, reported in this paper, was made to measure the absolute solubility at temperatures from room temperature through the melting point and make more accurate observations of the transition temperatures. APPARATUS AND METHOD The apparatus and method were essentially the same as those described in the previous work,1 as shown in Fig, I. At high temperatures, the small tube containing the thermocouple in the sample container A frequently broke off, so for some of this work the thermocouple was placed outside the sample container and protected by a quartz tube of about the same wall thickness as the sample container. No significant difference was found in the transition temperatures obtained in the two ways. The automatic temperature controller was used in these tests in the regions where there was little change in solubility with temperature. In the neighborhood of the transition points a continuously variable autotransformer was used instead of the automatic controller, and the power input to the furnace was adjusted so that the temperature increased or decreased at a very slow, uniform rate through the transition range. This procedure was followed because the temperature oscillations produced by the controller were too great compared with the transition range, and the transition points determined under such conditions were less accurate. ABSOLUTE SOLUBILITY Procedure and Results The absolute solubility of hydrogen in manganese could be determined most

Jan 1, 1946

By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.' Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.' For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969

By D. H. Davis

There are two general types of oil flotation processes, froth and bulk-oil. In froth flotation, the coal concentrates are removed in the form of a froth or foam composed of air, liquid, and solids. Mechanical or pneumatic agitation of a coal slurry with suitable frothing agent causes a selective action of the bubbles to the coal particles which are carried to the upper portion of the pulp in the flotation cell; the refuse is wetted by the water and does not rise with the froth, but goes out as tailings. The other type of flotation process, bulk-oil, consists of thoroughly mixing the slurry or pulp with 30 to 50 pct of its weight of oil. The coal agglomerates with the oil and drops to the bottom of the cell while the refuse is wetted by the water and is carried away in suspension. The concentrate granules may be screened and drained to 12 to 15 pct moisture. The minus 200 or 300-mesh is very effectively treated by this process. The Trent process is a bulk-oil type which has been used for coal cleaning on a commercial basis, but its use has been discontinued in this country. Froth flotation of bituminous coal should be subdivided into two distinct fields: (I) separation of a dry coal product such as recovered from an aspiration system; (2) separation of a minus 48-mesh slurry such as produced from a thickener in a wet cleaning plant. The capacities, performance, and general operating characteristics are very different in these two fields. The recirculated slurry in a washery becomes oxidized and is much harder to treat than a dry dust. It is difficult to clean a slurry containing an appreciable percentage of plus 48-mesh without also floating some high-ash clays minus 200-niesh in size. On the other hand, while working with an aspirated dust, good results have been obtained in floating coal as coarse as 3/16-in. Because of the relatively low capacity of flotation machines as compared with conventional fine-coal cleaners .and because of the greater quantity of reagents required to float coarse coal, there is usually no point in considering flotation on bituminous coal for anything coarser than approximately 48-mesh. In some coal-cleaning plants, good separations are being made down to 80 or even 100-mesh by a less expensive system of coal cleaning than flotation. The Pittsburgh Coal Co. carried out extensive tests on laboratory batch machines and on small units of both pneumatic and mechanical agitation types from 1930 to 1935 and have operated six, eight, and then twelve mill-size mechanical subaeration cells from 1932 to 1944 This paper will deal with some of the operating phases and results of coal-flotation practices as derived from this experience, and more specifically with the flotation practice at the Champion No. I preparation plant. The experience gained from the research and initial experimental work contributed greatly to the successful operation of the mill-sized flotation units at Champion.

Jan 1, 1949

By R. R. Nash, W. F. Sheely, E. D. Levine

ThiS note reports on the variation with temperature of critical stress for basal slip of binary solid-solution single crystals of indium and of thorium in magnesium. PROCEDURE Alloy single crystal spheres were acid machined to 3/8-in. diam cylinders with the basal planes of the crystals normal to the cylinder axis and then annealed at 810°K. Stress was applied parallel to the slip system, (0001) [1120]. Experimental details will be presented in another paper.' Two nearly equivalent' techniques of stressing were used. Stress on the magnesium-indium alloy crystals was increased by 1 g per sq mm at 1-min intervals, and the critical flow stress was defined as the lowest stress to pro-

Jan 1, 1960

By P. E. Busby, C. Wells, M. E. Warga

Fundamental data on the rate of diffusion of boron in austenite and solubility of boron in the a and y phases of iron and steel have been obtained from deboronizing experiments and provide partial explanations for some of the phenomena observed in boron steels. The rate of diffusion of boron is about the same as carbon in austenite. The solubility of boron in austenite at normal heat-treating temperatures is less than 0.001 pct. A partial tentative Fe-B phase diagram in the important low boron concentration ranges and an equation representing the diffusion of boron in austenite are presented. A LTHOUGH a search of the literature revealed ALTHOUGHthat boron diffusion had not been studied quantitatively and systematically prior to 1948, a few qualitative observations which were made by following the diffusion of boron into iron packed in ferro-boron1-3 suggest that boron obeys normal diffusion laws and that the rate of diffusion increases with increasing temperature. The claim of Cornelius and Bollenrath1 that boron does not appear to influence the rate of carbon diffusion has recently been substantiated by Wells, Batz, and Mehl.4 Calculations based on data from the paper by Campbell and Fayv indicated that the diffusion coefficient (D) for boron in iron at 900°C is approximately 3x10 sq cm per sec; a value of 2x10-7 sq cm per sec at 1038°C has been reported by Digges et al in connection with decarburizing experiments on a commercial boron steel containing 0.43 pct C. During the period 1948 to 1950 several diffusivity constant (D) values for the diffusion of boron in the y phase of iron and steel and a number of solubility values for boron in both a and y phases were reported. It was concluded tentatively as a result of Metals Research Laboratory studies that D values for boron in y and a phases are about the same as for carbon in the comparable phasesa and that carbon up to 0.4 pct did not affect the rate of diffusion of boron in y iron above 1000°C within the limits of experimental error. Whether saturation of the y or a phases with carbon would significantly affect rates of diffusion of boron through them was then and still remains in doubt. The best estimate of Q (activation energy) was reported to be about 25,000 cal, somewhat lower than that for carbon in y iron. The solubility of boron in y iron at 1000°C was thought to be higher than 0.004 pct B but not as high as a more recent analysis of available data shows it to be. The solubility of boron in a iron at 700°C was reported to be 0.0004 pct B, but it would not have surprised the authors if the true solubility value is actually lower than this. Breaks in diffusion curves which were not understood when first obtained prior to 1950 have now been recognized as indicating solubility limits, and these are included in the present paper. Experimental Procedure Two methods were employed in an effort to determine diffusion coefficients (D) for boron in austenite. Early experiments involved the use of welded couples prepared in accordance with the procedure of Wells and Mehl,' but when the results of these experiments proved to be unsatisfactory for calculating D values, studies were continued by means of deboronizing experiments. In both cases, boron analyses following the diffusion anneal were carried out spectrographically and all D values were computed using the Grube solution of Fick's law. The precision of the spectrographic method used proved to be about equal to that reported by Corliss and Scribner" —average deviation from the mean about 5 pct of the amount present when the boron content is 0.003 pct. Concentration-penetration curves obtained from spectrographic analyses of welded couples generally indicated that practically no boron was transported across the weld interface during the diffusion anneal. Furthermore the concentration-penetration

Jan 1, 1954

By C. C. Martin, M. C. Fuerstenau, R. B. Bhappu

Experiments revealed that quartz could not be floated in conductivity water at any pH with a long-chained sulfonate as collector. Various cations, Fe+++, Al+++, Pb++, Mn++, Mg++, Ca++, are shown to function as activators when the pH is such that the cation hydrolyzes. As the solubility product of the various cation-sulfonates was exceeded at the concentrations involved, precipitated cation-hydroxy-sulfonates, e.g. Fe (RSO3)2OH must be functioning as the collector in these systems. A number of interesting and important phenomena were revealed during a study of the response of beryl to sulfonate flotation.' Perhaps the most important observation is the effect of various cations on flotation response. Experiments showed that in the vicinity of pH 3.0, about three ppm Fe+++ increased recovery of leached beryl from about 60 pct to 100 pct, whereas about four ppm Ca+ + reduced the recovery from 60 pct to 2 pct. With the exception of ferric iron, all of the other cations investigated reduced flotation recoveries drastically at this pH. As postulated in the paper Sulfonate Flotation of Beryl,' even with low concentrations of polyvalent cations and sulfonate (on the order of one ppm), cation-sulfonates are precipitated immediately in solution. That is, blueish-white clouds were noted to form after given additions of salts to known solutions of sulfonate. Furthermore, it was also shown that one-hundred-fold more ferric iron than necessary to form the precipitated cloud had to be added to effect complete flotation. In other words, some form of solid ferric sulfonate was found to function as the collector in these systems. The form of the compound was suggested to be Fe(RCO3)2OH and that bonding to the surface occurs through the hydrogen of the hy-droxyl. As the form of this compound was shown to be dependent on the extent of hydrolysis of ferric iron, it is to be expected that ferric iron will be unique in some pH region. Further, if the presence of hydroxyl in the neutral precipitated compound is of primary importance, then other cations should function similarly but at different values of pH, since they will hydrolyze at different concentrations of hydroxyl ion. To determine whether the premise of hydrolysis is correct, the study was extended to quartz systems in the presence of various cations at various values of pH. EXPERIMENTAL MATERIALS AND METHOD Sodium alkyl aryl sulfonate was chosen as the collector for the experimental work. The reagent, sup plied as a courtesy sample by the Shell Chemical Co., has the following physical properties: Physical form Solid — Finely ground Sulfonate content, pct wt 95 to 97 Molecular Weight 450 to 470 Number of carbon atoms in hydrocarbon chain 25 to 30 Melting Point, OF 250 to 260 Solubility Soluble in water with gel formation at concentrations higher than 25 pct by weight sulfonate This particular reagent was chosen because of its high active sulfonate content, long-chain length, and solid form. With the exception of the frother and sulfonate, all other chemicals were of reagent grade quality. Conductivity water was used in the experimental work. This water, made by passing distilled water through an ion exchange column, had an average measured conductivity of one micromho. Experiments were conducted at room temperature in a small glass flotation cell with the following procedure: 1) A redetermined amount of water and salt solution (e.g. CaC12 . 2H2O) were combined and the pH adjusted to a given value. 2) A given amount of sulfonate was added so that final solution volume was 130 cc. 3) One drop of Dow 250 frother was added. 4) Five g of quartz were added and the system conditioned for five minutes. 5) The pH of the system was measured (termed flotation pH).

Jan 1, 1963

By N. J. Themelis, R. V. Flint

In a four-year period between 1973-76, the Metal Mining Division of Kennecott Copper Corp. conducted a company-wide program of operations improvement which involved line and staff personnel from all company functions. Specialist teams performed detailed studies of all operational aspects at Kennecott's four copper mines and concentrators, four smelters, and two electrore-fineries. The specific recommendations that resulted may transform the Metal Mining Division into the country's lowest cost producer of copper by the mid-1980s. In this article, N. J. Themelis and R. V. Flint describe the mechanics of MMD's integrated approach to operations improvement.

Jan 6, 1979

By J. W. Littleford

The Roan Antelope Copper Mines Ltd. are situated in the north central part of Northern Rhodesia, at an altitude of 4000 ft. and 13" south of the Equator. The town site (Luanshya) is well situated and enjoys among other things a really temperate climate for 10 months of the year. The two spring and summer months, October and November, while hot and humid, do not bring any great discomforts as compared with many other mining camps. Strictly modern brick homes, with electric lights, purified water, telephone and water-borne sewage, add to the comfort of the employees. A rainfall of approximately 60 in. per year furnishes ample water for both industrial and domestic purposes. The rainy season generally begins in October and lasts through until March. As much as 3 to 4 in. is recorded in 24 hr., but this offers no difficulties because the runoff is very rapid. The property is connected by a 24-mile branch line from Ndola with the main line of the Beira-Mashonaland and Rhodesia Railways Ltd. Practically all supplies from overseas are transported over this line from Beira, 1743 miles distant on the east coast in Portuguese East Africa. The mine output also leaves Africa from this port. Passenger service is principally via Cape Town or Durban, a distance of about 2100 miles to either port. The Imperial Airways maintain a service from Cape Town to Croydon, taking 9 days for the trip. Connections can be made with this service at Broken Hill, 150 miles south of Luanshya, by either rail or automobile. Thus, after several days of travel through virgin bush, a visitor arrives at a typically modern town site in the heart of Africa. Every development in mining, milling and smelting practice is used to advantage. Plan of Mill The practice in the three principal phases of the production of copper from the ores of this company have been published from time to time. Milling practice, however, is continually changing and what may be

Jan 1, 1935