Search Documents

By Frank Foote, E. R. Jette

Precision lattice-constant measurements have been widely used in the study of cubic solid solutions but as yet have been rarely applied to noncubic solid solutions. (See, however, references I and 2.) With the high precision at present attainable in the measurement of lattice constants, the X-ray method should be readily applicable to noncubic solid solutions. In the work reported here, hexagonal close-packed magnesium was used as the solvent and either lead, bismuth or gold as the solute. In the magnesium-lead and magnesium-bismuth systems the a and c lattice constants were determined as a function of composition, densities were calculated from these lattice-constant data, these theoretical densities were compared with those directly measured and the solid solubility limit was determined on quenched specimens over a considerable range of temperature. In the magnesium-gold system, the solid solubility is very small but we have obtained an indirect check on the solubility limit previously reported. Materials and Preparation oF the Alloys The magnesium used was obtained from the Aluminum Company of America and was 99.987 per cent pure. Impurities as reported On the label were: Fe, Al, 0'004 per cent; Si, 0.009 per cent; Zn, trace; Cu, Pb, nil. The bismuth was Merck's analytical grade, minimum purity 99.95 per cent. Maximum impurities as listed on the label were: Fe, 0.008 per cent; Pb, 0.010 per cent; Ag, 0.010 per cent; Cu, 0.005 per cent; Sn, 0.003 per cent; Sb, 0.00; As, 0.000; S, 0.01 per cent. The gold was purified by double precipitation with sulphur dioxide. The lattice constants of these three metals have been previously reported.3 The lead used was test lead, silver free and with a maximum of 0.10 per cent heavy metal impurities. The lattice constant 01 this lead has been measured and found to be 4.94057 ± 0.00016 at 25°C. The alloys were prepared by melting together weighed amounts of the constituent metals in magnesia-lined alundum crucibles under an atmosphere of hydrogen purified by passing over magnesium heated to 500°C. The magnesia lining prevented contamination 01 the alloys with aluminum. Vacuum melting could not be used because of the volatility of magnesium. A high-frequency induction furnace was used for the melting operation and the stirring action of the current resulted in thorough mixing of the constituents. The melts were allowed to freeze in the crucible, the ingots obtained weighed about 10 grams. An extremely thin white film formed on the surface of the melts, sometimes covering only a part of the exposed surface. The ingots were filed clean, placed in small iror crucibles with close-fitting lids and indi. vidually sealed into Pyrex glass tubes Before sealing off, the tubes were alter

Jan 1, 1941

By R. W. Raymond

Since the foregoing paper (see p. 387) was printed, I have received the decision of Judge William E. Church, of the first District Court of Dakotah, in the case of Michael Duggan et al. v. John H. and Frank J. Dnvey (Silva Terra—Sitting Bull case), published in full in the Black Hills Weekly Pioneer of August 9th, 1584. The journal mentioned gives also several interlocutory decisions rendered in earlier stages of the case; but I shall quote here only so much of the final decision as bears upon the .construction of the Revised Statutes concerning the apex, the end-lines, and the extra-lateral mining right, together with a sufficient statement of the facts of the case to explain the scope of the decision. " This is an action in equity, brought in the first instance to restrain a threatened trespass by the defendants upon certain mining property in the possession of the plaintiffs, known as the ' Silver Terra' claim ; the allegation being that the defendants were about to enter, through underground workings, the ground of the plaintiffs, and remove therefrom valuable bodies of silver ore. " The answer of the defendants, admitting the acts constituting the alleged threatened trespass, further averred that they had, in fact, at the time complained of, reached and passed, in their underground workings, throngh and beyond the vertical side-line of the Silver Terra claim, and therenpon justified the acts complained of, and claimed the right to pursue their workings into and through the Silver Terra ground, by virtue of their alleged proprietorship of a vein, lode, or ledge of rock in place, hearing silver, having its top or apex within the lines of a certain other mining claim called the ' Sitting Bull,' of which they claim to be the owners, which vein, lode, or ledge extended in a continnons body of mineral-bearing rock from such top or apex to the ground in controversy, and constituted the body of ore in dispute; and that it was in the pursuit of this vein, lode, or ledge in its downward course that they had passed beyond the vertical side-lines of the Sitting Bull claim, and for some hundreds of feet beyond, into the ,ground in controversy " Subsequently, a supplemental complaint was filed, setting up the entry into plaintiffs' ground by the defendants, and their claim of right to do so, and asking fnrther relief by a decree restraining the assertion of such claim, and quieting the title of plaintiffs. "The case was tried before the court without a jnry..... " Custer hill, upon which these claims are located, is situated in the village of Galena, in Bare Butte mining district, in this county. The village lies at the base of the western slope of the hill, which presents a lateral face from south to north

Jan 1, 1884

By R. M. Brick, F. L. Vogel

THE elementary mechanism of deformation in the body-centered cubic metals has been a subject of dispute for many years. If the problem were merely that of designating the crystallographic plane or planes of slip, the solution would have appeared long ago. However, there must be greater differences in the deformation behaviors of the body-centered and face-centered types than the differences in their lattices would suggest. The lines of slip formed on the polished surface of a strained face-centered cubic metal conform to glide over a single plane of the crystal. Slip in body-centered cubic iron, however, is frequently observed as curved and forked lines which could not possibly define a single plane of atoms. This alone is sufficient reason to expect different modes of deformation to operate in the two lattice types. The literature in this field now has generally accepted the proposition that {110), {112), or (1231 planes will act as slip planes in iron. It is essential that the experimental evidence supposedly supporting this proposition be critically examined. Taylor and Elam1 in 1926, using relatively small single crystals, determined the operative slip systems by measurements of the distortion of a grid engraved on the specimens prior to deformation. Their results indicated that shearing had taken place in the close-packed direction on a plane adjacent to or coinciding with the plane of maximum shear which contained the slip direction. This led the authors to propose a theory of noncrystallographic or banal slip. The authors considered an alternate rationalization of banal glide. Slip on two (1101 planes or possibly two {112} planes containing the same <1ll> direction could produce the wavy slip lines. By employing plane segments of varying widths, the integrated plane could take any position in the <111> zone. They rejected this explanation, however, feeling that the preponderance of evidence was against it. Taylor&apos; continued the investigation of the plasticity of the body-centered cubic lattice on ß brass. He reasoned that the resistance to shearing of a given plane in the zone of the slip direction was a function of the angle between the glide plane and the closest (110),: P F=—cose sine cos(X —?) [1] where F is the resistance to shear; P, the axial load at yielding; A, the cross sectional area; e, the angle between slip direction and load axis; x, the angle between plane of maximum shear containing the slip direction and the (101) pole; and ?, the angle between observed glide plane and the (101) pole. Differentiating Eq. 1 and rearranging, dF — = tan(x-?) d? [2] F which expresses the variation of the shear resistance with the angle $. Integrating this equation between the limits 0 and ? yields In F/F0 = ?0?tan(x— ?) d? [3] Here, F, is the resistance to shear of the (110) plane and F is the resistance to shear of a plane $ degrees from the (110). Thus, the variation of shear resistance with $ can be calculated from an experimentally measured x vs $ relationship. Fahrenhorst and Schmid8 sed several methods, none of them involving direct observation, to determine the glide system in ferrite. They determined the variation of critical resolved shear stress with

Jan 1, 1954

By G. W. Sheary

At Bethlehem&apos;s Grace mine&apos;s 6000-tpd pelletizing plant a cascade control system is utilized to approach a constant magnetite filter cake moisture, a critical factor in obtaining quality green pellets. Variables being controlled by instrumentation are filter feed solids, filter tub level, first and second stage pump sump levels and thickener sludge level, all at varying feed rates. Startup difficulties, modifications and contemplated additions to obtain closer control of the moisture are discussed. Situated 45 miles west of Philadelphia and 50 miles southwest of Bethlehem Steel Co. &apos;s Beth-lehem plant, the integrated Grace mine facilities produce 4000 tpd of high-quality iron ore pellets. Startup of the Grace mill was in November 1958, and iron concentrates were shipped until March 1960, when the pellet plant went into operation. The underground mine, when fully developed, will hoist about 9000 tpd, including development rock. The crude ore, which has an iron content of approximately 42%, is magnetically cobbed and crushed in closed circuit with %-in. slotted vibrating screens. The ore is washed and screened in the mill and the 1/4-in. screen product is again cobbed prior to feeding to the rod mills. Grinding is done in rod mills, and in ball mills that are in closed circuit with 30-in. cyclones, to 1% on 100 mesh and 65% -325 mesh. The ground ore is magnetically concentrated by three-drum permanent-type finisher magnets to 67% Fe. The magnetite concentrate is pumped from the mill to a 50-ft thickener in the pellet plant. The thickened magnetite concentrate is relayed to the filters through a two-stage pump arrangement. The filter cake is fed by belt from filter concentrate bins to mixer-muller belts where it is intimately mixed with bentonite and a slight amount of water for moisture control. The fluffed concentrate then drops into balling cones. The green pellets from the balling cones are fed in a prescribed feed pattern to shaft furnaces through the use of shuttle car mechanisms. The green pellets are dried, heated to 2500°F and cooled to 1200°F as they descend through the furnace and into pellet coolers where the pellets are further reduced in temperature to 250°F. Heat is recovered in the cooling process through the use of air-to-air heat exchangers. The cooled pellets discharge on a rubber conveyor belt and are transferred to 6000-ton pellet railroad loading bin. The final pellet product consists of 90% +&apos;1/4 in. material (after tumble testing1) and contains 66% Fe plus 3% silica. It has been the usual practice to maintain constant filter tank level by pumping an excess constant volume and using a moveable fishtail splitter to divert the desired amount of slurry to the filter tank. The excess from the fishtail and from the filter overflow pipe, which maintains a constant level, is returned to the source. At the Grace mill, tremolite builds up in the pipelines when pumping heavy magnetite concentrate slurries, making it necessary to use polyvinyl

Jan 1, 1962

By Ernest L. Ohle

The newly opened Hayden Creek lead mine represents a variation from the usual Southeast Missouri type. Galena mineralization occurs in sandy dolomite cementing a conglomerate of granite boulders and in cracks in the boulders. The conglomerate occurs at the base of the Bonneterre formation on the slopes of two buried pre-Cambrian knobs. IN 1943 diamond drilling from the surface in an area 2 miles southwest of Leadwood, Mo., discovered a lead deposit of a markedly different character from the usual southeast Missouri type. Subsequent drilling of about 500 holes indicated several million tons of ore, and in 1950 a 701-ft vertical shaft was sunk into the orebody. This paper describes the geology of this interesting occurrence insofar as it is known from the drilling and the small underground exposure at the bottom of the shaft. Geology The location of the Southeast Missouri Lead Belt and of the Hayden Creek property are shown in Fig. 1. As shown here, there are two separate producing areas, one from which the larger tonnage has come, located near Bonne Terre, Flat River, Desloge, and Leadwood, and the other to the south around Fred-ericktown and including famous old Mine LaMotte. The best published description of Lead Belt geology is by Tarr.* In pre-Cambrian time in this area, an assemblage of granites and rhyolitic flow rocks was eroded to a mature topography. Sedimentation, beginning in the Upper Cambrian, filled in the valleys and gradually covered even the highest hills. The first formation deposited was the La-motte sandstone; it is successively overlain by the Bonneterre dolomite, the principal lead-prodbcing formation, then the Davis shale. the Derby-Doerun limestone, and a succession of Cambro-Ordovician cherty dolomites. Several of these formations may be found in direct contact with the pre-Cambrian as their deposition progressively overlapped the older rocks on the flanks of the igneous knobs and ridges. Immediately overlying the pre-Cambrian there is, not uncommonly, a thin basal conglomerate of granite or porphyry boulders, which is incorporated into the overlying sediments. Deposition of the lower part of the rock section was fairly continuous, and the Lamotte sometimes grades almost imperceptibly into the lower sandy Bonneterre. Since the sediments were deposited on an uneven floor, they tend to reflect the irregularities in that floor. Most of the steep dips found in the district, that is, dips in excess of 10°, are original dips and not caused by deformation. Such domelike structures in the sedimentary rocks around the igneous knobs have localized a considerable number of the orebodies in the district and particularly those in the Frederick-town area. Many of the larger orebodies, however, have no close relation to the pre-Cambrian topography. Most of the lead production has come from the lower 150 ft of the Bonneterre formation, where disseminated ore spreads laterally parallel to the bedding for great distances. Average stoping height is about 20 ft, but in a few places there are stopes over 175 ft high.

Jan 1, 1953

By James F. Watson, Jack L. Christian

The austenite to martensite solid state phase transformation in the 300 series austenitic stainless steels was studied over the temperature range of 788° to -423°F. The primary variables controlling this transformation are temperature, plastic strain, and chernical composition. Consequently, temperature effects were studied by measurements at 78", -100°, -320°, ad -423°F; plastic strain was controlled by cold-rolling the alloys varying amounts between 40 and 80 pet; and chemical compositions were varied by using 301, 302, 304 ELC, and 310 stainless steel alloys which exhibit varying degrees of austenite stability. The martensite contents of various alloys were correlated with several mechanical properties including yield and ultimate tensile strength, elongation, and notched tensile strength (Kt = 6.3). The yield and tensite strengths generally increased with increasing martensite content, but ) no correlation was observed between elongation and martensite content. The notched/un-notched ratio (Kt = 6.3) at -423°F exhibited a maximun at about 65 pct martensite. Attempts to correlate austenite stability (as measured by the Ms temperature) with both martensite content, and incremental increases in martensite content resulting from tensile testing were generally unsuccessful because the variable of cold Work could not be separated. As a result, only a general correlation of these variables was obtained. A (111) pole figure of austenite in a cold-rolled 301 stainless steel mas prepared an attempt to further investigate directionality as exhibited by mechan- ical properties. Yield strength was correlated with this pole figure, but ultimate and notched tensile strengths were not. 1 HE literature contains a wide variety of references pertaining to the austenite to martensite solid state phase transformation in austenitic stainless steel, see references 1 through 18. Discussions of the crystallography and kinetics of this transformation are given in references 2, 7, 8, &apos;and 11, while further discussions of austenite stability and hardening mechanisms are given in references 1, 3, and 10. Two important processing variables involved in this reaction are the degree of cold work and the temperature at which cold work is performed, and the nature of these effects are outlined in references 4 and 12, and 15 and 16 respectively. The latter two references deal primarily with cold rolling conducted at subzero temperatures. The effect of chemical composition on the austenite to martensite reaction was treated in detail by Eichelman and Hull, and they determined an equation for the M, temperature of this type of steel which included the effects of nickel, chromium, carbon, nitrogen, silicon, and manganese.5 Previous studies have shown that austenitic stainless steels of AISI types 301, 302, 304ELC, 310, and 301-N exhibit mechanical properties between 78" and -423"~ that are microstructure dependent, and the dependence of this microstructure on chemistry, temperature, tensile stress, and prior deformation is in general accord with previous investigations which have measured the effects of each of these variables on structure, or more specifically, the austenite-to-martensite transformation.lg The behavior of fully stable alloys, such as ATST type 310, at cryogenic temperatures is

Jan 1, 1962

By Ernest L. Ohle

The newly opened Hayden Creek lead mine represents a variation from the usual Southeast Missouri type. Galena mineralization occurs in sandy dolomite cementing a conglomerate of granite boulders and in cracks in the boulders. The conglomerate occurs at the base of the Bonneterre formation on the slopes of two buried pre-Cambrian knobs. IN 1943 diamond drilling from the surface in an area 2 miles southwest of Leadwood, Mo., discovered a lead deposit of a markedly different character from the usual southeast Missouri type. Subsequent drilling of about 500 holes indicated several million tons of ore, and in 1950 a 701-ft vertical shaft was sunk into the orebody. This paper describes the geology of this interesting occurrence insofar as it is known from the drilling and the small underground exposure at the bottom of the shaft. Geology The location of the Southeast Missouri Lead Belt and of the Hayden Creek property are shown in Fig. 1. As shown here, there are two separate producing areas, one from which the larger tonnage has come, located near Bonne Terre, Flat River, Desloge, and Leadwood, and the other to the south around Fred-ericktown and including famous old Mine LaMotte. The best published description of Lead Belt geology is by Tarr.* In pre-Cambrian time in this area, an assemblage of granites and rhyolitic flow rocks was eroded to a mature topography. Sedimentation, beginning in the Upper Cambrian, filled in the valleys and gradually covered even the highest hills. The first formation deposited was the La-motte sandstone; it is successively overlain by the Bonneterre dolomite, the principal lead-prodbcing formation, then the Davis shale. the Derby-Doerun limestone, and a succession of Cambro-Ordovician cherty dolomites. Several of these formations may be found in direct contact with the pre-Cambrian as their deposition progressively overlapped the older rocks on the flanks of the igneous knobs and ridges. Immediately overlying the pre-Cambrian there is, not uncommonly, a thin basal conglomerate of granite or porphyry boulders, which is incorporated into the overlying sediments. Deposition of the lower part of the rock section was fairly continuous, and the Lamotte sometimes grades almost imperceptibly into the lower sandy Bonneterre. Since the sediments were deposited on an uneven floor, they tend to reflect the irregularities in that floor. Most of the steep dips found in the district, that is, dips in excess of 10°, are original dips and not caused by deformation. Such domelike structures in the sedimentary rocks around the igneous knobs have localized a considerable number of the orebodies in the district and particularly those in the Frederick-town area. Many of the larger orebodies, however, have no close relation to the pre-Cambrian topography. Most of the lead production has come from the lower 150 ft of the Bonneterre formation, where disseminated ore spreads laterally parallel to the bedding for great distances. Average stoping height is about 20 ft, but in a few places there are stopes over 175 ft high.

Jan 1, 1953

By G. H. Kennedy, H. E. Criner

CYCLONE thickeners are "hydraulic centrifuges" designed either to produce a maximum practical separation between the water and solids of a feed slurry or to classify the slurry solids according to particle settling rate. The possibilities of utilizing the thickener to "close" plant water circuits have been investigated. Since the thickener becomes an integral part of the plant water circuit when installed, the basic means by which the solids content of all circulating water systems must be controlled is reviewed. All coal not separated from the circulating water by means of dewatering screens or settling devices must be bled from the plant at the same rate as they are being fed or created by degradation. If this were not true, the circulated volume would finally be completely filled with solids. If the rate of bleed is low, the solids concentration in the bleed and circulating water generally will be high. To keep a reasonable circulating water concentration, large amounts of fresh water must be supplied and the bleed rate must be high. These conditions are usually undesirable because of the difficulty in securing fresh water, the loss of large quantities of coal, and the pollution of nearby streams. Thickeners are the primary stage in the separation of the water contained in the bleed from the coal. Since a thickener, when operating with reasonable efficiency, usually cannot be expected to deliver an underflow containing less than 50 pct water, secondary dewatering devices such as a slurry screen or vacuum filter must be used to separate additional water from the bleed. The surface area required by the filter or screen will be nearly proportional to the total water which must be handled, and therefore the thickener becomes necessary to hold down the original cost. The water separated from the coal is then returned to the plant circuit to maintain the water balance and thus becomes the source of fresh water. It is not necessary to return clear water to the plant to maintain control of the circulating water concentration. It is only necessary that the bleed dewatering devices remove coal in all sizes at a rate equal to that at which these sizes are entering the circulating water. However, practically speaking, in order to maintain low solids concentration, it is usually necessary that the thickener have good recovery characteristics on bituminous coals in those sizes down to 400-mesh. The thickener can remove the smaller sizes from the closed-circuit system at the "solids in" rate and prevent their "build up" in the circulating water as shown in Fig. 1. With the portion of the feed water going directly to the underflow, comes the very fine solids not concentrated by the cyclone. All the larger solids are removed from the feed and delivered in a concentrated condition at the underflow. To apply thickeners with some reasonable assurance that operating requirements will be met, it is necessary to know the rate at which solids of all sizes must be removed from the circulating water and to know the thickener characteristics. The required removal rate of fine solids not recovered by other dewatering devices may be estimated from the size distribution and tonnage of the plant feed with a reasonable allowance for degradation in the circulating water system. A more reliable estimate may be secured by sampling the plant bleed water during a constant load period.

Jan 1, 1952

By U. F. Kocks

SINGLE slip and a single parallel array of edge dislocations have been obtained in silicon single crystals by homogeneously bending them in a four-point dead-loading device at 1000°C around the [211] axis with [253.] as the tensile axis which encloses an angle of 40° with the glide plane. Other orientations or lower temperatures proved unsuitable. The homogeneity of the bending was checked by the method shown in Fig. 1. The chemically polished specimen was exposed to parallel light from a microscope-stage lamp. The sharpness of the focus of the reflected light is an approximate measure of the circularity of the sample. This method permitted the determination of the actual radius of bent specimens within 10 pct accuracy. The etching solution developed to show up dislocations consisted of the following volume parts: 2 HF, 1 HNO,, 2 CH,COOH, 1 a solution of 5 wt pct of CuNO, in water (Rosi&apos;). The acetic-acid content was adjusted to produce fine well-defined etch-pits in about 2 min at room temperature. The effectiveness of the etch did not depend on the crystal-lographic orientation of the face etched. The number of etch pits produced after a given deformation was checked in the usual way against the Cahn formula&apos; and showed good agreement. As it is to be expected from the orientation of the primary system there are slip steps on the top and bottom faces but not on the side faces (perpendicular to the bending axis), whereas etch pits appear on the side faces but not on the top and bottom faces. This is different only for occasional dislocations of a secondary glide system. All the micrographs included have been taken in places where the most of secondary glide could be seen. From this it is evident that in the homegeneously deformed region the number of secondary dislocations was less than 1 in 1000 of the primary type. Dislocation Distribution—A series of tests with varying amounts of deformation is shown in Figs. 2(a-c). An observation that can readily be made from these pictures is that the linear density of dislocations within slip lines is relatively constant and independent of the amount of deformation. "Slip line" in this context is understood to mean a line that is a straight connection of individual etch pits. The heavily pitted bands which can be seen in each of these three pictures may be resolved fairly definitely, at higher magnifications, into many "slip lines" the distance between them being of the order of 0.5p The distance between dislocations in slip lines is of the order of 2p and it is also fairly constant in going from the neutral zone outward. The higher over-all dislocation density in the outer regions of any sample and the higher total number in a more heavily deformed sample, are effected by a larger number of "slip lines." The relative constancy of the dislocation distance within an individual slip line is surprising. The absence of pile-ups" may imply, if there is no rear- rangement on unloading," that there are no substantial obstacles to slip in this case. It seems that the equilibrium distribution of the dislocations in each active slip plane under the higher external stress on

Jan 1, 1959

By Robert G. Johnson, Richard J. Prosen

THE present work was done in connection with a program for investigating metal-to-ceramic braze techniques using the well-known reactivity of titanium with certain ceramic oxides. The investigation extended over the range of 0 to 30 pct Ti. The indium was obtained from the Indium Corp. of America and was specified to be 99.97 pct pure. The titanium was supplied by Metals Disintegrating Co. and was stated to be 99.5 pct pure. Each 2 to 4 g quantity of the alloy compositions studied was prepared using a mixture of 300 mesh powders pressed into pellet form. The pellets were heated in thin-walled molybdenum crucibles using a resistance-wound furnace in a vacuum less than 10-4 mm of Hg. Little reaction occurred between the molten alloy and the crucibles at the temperatures and short time intervals used. Only slight spectroscopic traces of molybdenum were found in the melt after a typical period of heating. The points shown on the phase diagram of Fig. 1 represent thermal arrest measurements. The phase boundaries shown are consistent with the thermal arrest and X-ray data obtained. The temperatures were determined using a Pt-Pt 10 pct Rh thermocouple with the junction spot-welded to a short molybdenum rod. The rod was almost completely immersed in the liquid metal, so that good thermal contact with the melt was achieved. The small mass of the crucible and its contents made it possible to obtain many heating and cooling curves in a few minutes time, an advantage which helped to minimize the effects of indium evaporation at the higher temperatures. A Brown strip chart recorder was used to display the thermal arrest curves. To check the technique, the melting point of 99.999 pure Al was measured and found to be within 1 of 660.2c, the accepted melting point. The upper limit of temperature with this technique was about 900°C beyond which the evaporation rate of indium became great enough to alter appreciably the alloy composition during the runs. A peritectic transition was found at 796°+ 5°C from 1.5 to 30 wt pct Ti. It was not found at 0.5 or 1.0 pct. A small super-cooling effect was observed. The melting-point transition to the B + L phase was found up to 20 pct Ti but not at 25 pct. Within the 1 deg accuracy of the measurement, the transition temperature was that of pure indium, 156°C. The liquidus line to the left of the 1.5 titanium point was located only approximately. The two crossed circle points at 1.0 and 0.5 pct Ti place a lower limit on the liquidus line and were determined by observing visually the cessation of vibrations in the melt caused by the damping effect as B-phase crystals were formed during cooling. The B-phase boundary was found at 23.8 pct Ti by X-ray analyses of small single crystals of the B phase isolated from 2 pct Ti melts. The compound was found to be Jetragonal with lattice dimensions of c = 3.052A and a = 10.094W. From the unit cell dimensions and the measured density of 6.42 i 0.05 g per cc, the compound was determined to be In4Ti3 which has 23.8 pct Ti. The calculated density of 6.44 g per cc is obtained assuming 2 mol

Jan 1, 1962

By Alfred Siegel

Mineral pigments give color, opacity, or body to paint, stucco, plaster, mortar, cement, linoleum, rubber, and similar materials. They must be finely divided, substantially insoluble, and generally inert for such uses. Inorganic pigments may be grouped somewhat arbitrarily as follows: A. Natural mineral pigments dug from the earth. 1. Those consisting mostly of iron oxides, such as hematite and limonite. 2. Those containing large amounts of clay or noncoloring matter, such as ocher, sienna, umber, and colored shales. 3. Those whose color is not due to iron oxide, such as Vandyke brown (including sap brown, an alkali extract of Vandyke brown), graphite, and terre verte. B. Synthetic pigments. 1. Those containing iron oxide as the essential coloring matter, such as "pure" reds, yellows, and blacks, and Venetian reds. 2. Those not containing iron oxide, but rather such compounds as lithopone, zinc white, titanium white, ultramarine, Prussian blue, and the like. Only groups A and B-1 are discussed here. All the pigments in those two categories, except Vandyke brown, sap brown, and some of the carbonaceous slates, contain, as their essential color constituents, one or more compounds of iron; namely, an oxide-limonite (2Fe2O3.H2O to Fe2O3.4H20), hematite (Fe2O3), or magnetite (Fe2O3.FeO). Man&apos;s first permanent coloring materials were earth pigments-the ochers, iron oxides, and various iron-stained clays. The caves occupied by prehistoric man and the arts of the ancient Chaldean, Egyptian, and Cretan civilizations bear mute witness to this and also testify to the beauty and permanence of earth colors. As the Roman era developed, earth pigments were pushed from their pre-eminent position by white lead and red lead and in the Middle Ages by zinc oxide. Today, of course, the number of acceptable pigments is very large and on a value basis the group of natural and synthetic earth pigments stands forth with $16,000,000 per year; it is surpassed by titanium, lead and zinc pigments. Of this sum,21 natural pigments supplied 31 pct of the tonnage and 16 pct of the value of the total finished pigment in 1957, the remainder representing the tonnage and value of sales of the synthetic iron oxide colors. The average value of finished natural pigments in 1958 was $80.62 per ton. The average value of manufactured pigments in the same year was $202 per ton. Of the 60,000 tons of manufactured colored pigments sold in 1958, the reds comprised 76 pct of the market and the yellows 20 pct. The reds furnished 68 pct of the value and the yellows 24 pct. Of the finished iron oxide pigments (natural and manufactured) sold in 1958, the reds dominated the market with 66 pct of the quantity and 63 pct of the value; yellows supplied 17 pct of the quantity and 20 pct of the value, and browns furnished 11 pct of the quantity and 10 pct of the value. The average value of the reds was approximately $152, and the average value of the yellows $190 per ton. The highest valued pigment in 1958, with almost 12 pct of the total tonnage and 21 pct of the value of the iron oxide pigment market, was manufactured red from calcined copperas valued at $286 per ton.

Jan 1, 1960

By J. T. Norton, N. J. Grant, A. M. Gervais

An investigation of the creep deformation of coarse-grained high-purity aluminum at temperatures approaching the melting point permitted the formulation of a theory of subgrain formation. Subgrain boundaries were found to be formed by two different processes: kinking and polygonization. Polygonization is considered as the main factor in subgrain formation. SINCE "slipless flow" was first discussed in detail by Hanson and Wheeler,&apos; many studies have been undertaken to determine how metals deform at high temperatures. Several types of observations have been reported. Jenkins and Mellor,² working on the creep of mild steels and various grades of commercial irons, found metallographic evidence of a kind of substructure within the grains after deformation at high temperatures. Homes" observed after creep deformation of steel at high temperatures that the original X-ray spots were sharply divided into several small ones. The same phenomenon was reported by Hirst4 from his studies on lead and later by Crussard5 from his work on aluminum. The works of these investigators demonstrated beyond any doubt that the splitting of the X-ray spots was due to the fact that the grains underwent a division into subgrains during deformation at high temperatures. Since then, numerous experiments have been undertaken on aluminum in order to determine the mechanism of formation of subgrains. Research workers can be divided, for the purpose of discussion, into two different groups as regards thinking on subgrain formation. On one hand, based on the work on polygonization by Cahn,6 Guinier and Lacombe,7 Greenough and Smith," Crussard,10,11 and Servi, Norton, and Grant," it was concluded that subgrain formation was a consequence of the simultaneous effects, first, of inhomogeneous deformation which produced bending of the lattice, and second, polygonization. On the other hand, Wood and coworkers13-16 based their work on the results of an earlier report" which dealt with crystallite size and a fragmentation theory. It is interesting to note that while Greenough and Smith8 and Wood et al. performed similar experiments, their conclusions were quite different. Wood et al. did not recognize polygonization as a fundamental mechanism and said that aluminum, at the beginning of the deformation, fragmented immedi- ately into subgrains in order to permit deformation of the metal, the number of these subgrains being a function of strain rate and temperature. They concluded that deformation of grains occurred by flow along the subgrain boundaries. In view of the contradictory conclusions, it would appear that the data were not explicit enough to provide an unambiguous conclusion. It appears that the techniques by which most of the results were obtained, namely, X-ray work, were not enough by themselves to solve the problem. Another approach was needed. In the present research, therefore, an extensive metallographic study was planned to supplement the X-ray work. The importance of revealing the subgrain boundaries metallographically was realized, and this will explain the extensive development and use of etching techniques. In order that subgrains would be considerably larger and therefore more readily visible under a microscope, the creep experiments were performed at very high temperatures approaching the melting point of aluminum. Development of Experimental Technique Creep tests were run at constant load on high purity (99.995 pct) aluminum specimens having a very coarse grain size. None of the specimens was run to fracture. The specimens were originally round (diameter, 0.187 in.; gage length, 1 in.) and had parallel flats milled in the gage section to permit

Jan 1, 1954

By J. G. Richardson

The performance of laboratory water floods is compared with the flooding behavior calculated by the Buckley-Leverett techniques from steady-state relative permeability-saturation relations. Both the steady-state and unsteady-state experiments were conducted on the same sand-packed column. Relative permeabilities were calculated by the Welge technique from the unsteady-state waterflooding displacement experiments and compared with those measured by steady-state techniques. An evaluation of the various calculation procedures was made. It was demonstrated that steady-state relative permeabilities could be used to calczcJate waterflood performance. INTRODUCTION To calculate the waterflooding behavior of a given reservoir, relative permeability-saturation relations of the reservoir rock are required. These relative permeabilities are commonly measured on core samples by steady-state experiments such as the Penn State technique.&apos; The relative permeabilities obtained in steady-state experiments are calculated from oil and gas flow rates and pressure drops measured under conditions of equilibrium distribution of oil and water in the pore spaces with slow approach to equilibrium. On the other hand, in water floods the water saturation at a given point changes rapidly with time as the flood front passes. Extensive research2 has shown that the steady-state relative permeabilities to oil and water are independent of the rate of flow and the fluid viscosities. Research has also demonstrated that the waterflooding performance of homogeneous sands uniformly contacted by water is independent of rate when capillary pressure gradients, which are important in short laboratory columns, are made negligible. However, there is little experimental data in the literature comparing relative permeabilities calculated from steady-state flow experiments with those calculated from flooding experiments. In this paper, the production data of two water floods and the relative permeabilities calculated from a series of steady-state experiments on an unconsolidated sand column are presented along with the comparisons calculated by the Buckley-Leverett and by the Welge techniques. The purpose of this study was to determine if steady-state relative permeabilities could be used to predict the waterflooding performance. This study also permitted an evaluation of the Buckley-Leverett and Welge calculation procedures and allowed an insight into the nature of microscopic displacement of oil by water. EXPERIMENTAL APPARATUS AND PROCEDURE The apparatus used in this investigation was a Lucite column 1 ft long and 11/2 in. in diameter. A drawing of the apparatus is shown in Fig. 1. Six pressure taps were evenly spaced along the top of the column to measure the oil pressures. Three pressure taps fitted with small porous disks were spaced along the side of the column to measure water pressure. Water was admitted to the inflow face of the sand through a porous disk while oil was admitted through a hole in the porous disk and distributed to the face of the sand by grooves machined in the porous disk. Retainer screens of 325-mesh stainless steel were cemented over the inlet and outlet ports and the pressure taps to prevent loss of sand. The column was packed with a clean dry sand all of which was finer than 200 mesh. Next, the sand was saturated with a solution of 150,000 ppm sodium chloride solution. The column was weighed dry and water-saturated to obtain data for the calculation of the pore volume. A 151-cp oil was then injected into

Jan 1, 1958

By D. O. Wyble, L. O. Bacon

THERE has been considerable speculation among mining geologists and mining men in general as to the relative merits of gravity methods in iron-ore exploration. Most of the investigations which have been carried out in recent years have been done by mining companies, and few if any of the results have been published. Three gravity surveys have been made in the Iron River-Crystal Falls area,&apos; " one by the U. S. Bureau of Mines, with inconclusive results, and the other two by Radar Exploration Co. for the Cleveland-Cliffs and the M. A. Hanna companies, with results not known to the writers. Both the last-mentioned surveys were detailed investigations, the stations being spaced as close as 10 ft along traverses,&apos; and were made to determine the feasibility of locating iron ore by gravitational methods. Because of the presence of a large body of ore already extensively drilled, Dr. Harold L. James of the U. S. Geological Survey, Iron River, Mich., suggested that a further test of gravitational methods of exploration be made in the Round Lake area of Iron County, see Figs. 1 and 2. This survey indicated a considerable regional gradient and led to a study of the surrounding gravity field and its relation to the major structural features of the syncline within which the iron formation lies. The southwestern part of Iron County presents a series of hills and hollows elongated in a roughly north-south direction. The bedrock topography is of pre-glacial origin. Relief is moderate; a maximum elevation difference of approximately 350 ft was observed during the survey. Major drainage is dendritic with the larger streams: the Brule to the south, the Paint to the north, and the Iron in the central part. Hills are thickly grown with hard- woods, and lowland areas, not under cultivation, are usually covered by second-growth softwoods. The area covered in this paper includes the southern half of Iron County, Mich., with a deep synclinal basin occupying the central part of the area, and the southeast corner of Gogebic County, immediately to the west of Iron County. The upper Huronian iron formation, slates, and graywackes which form the synclinal basin rest upon a greenstone basement. The basin has not been completely outlined by exposures, drill records or other means, as outcrops are scarce and the thick mantle of glacial drift makes geological investigations extremely difficult. Glacial drift varies in depth up to 300 ft or more. The drift is usually thickest under the hills and is thinnest in the depressions and along drainage courses where most of the bedrock exposures occur. The area over which gravity investigations were made is almost, entirely covered by glacial material. Bedrock of the basin consists of a complexly folded series of iron formation, slates, and graywackes. One of the series of slates has a high magnetic susceptibility due to the fine-grained magnetite it contains. This formation can be detected readily. by magnetic methods and provides a marker horizon which can be easily followed. The magnetic slates are stratigraphically above the iron formation, and much of the geological interpretation of the area is based upon the magnetic anomalies they produce.

Jan 1, 1953

By L. O. Bacon, D. O. Wyble

THERE has been considerable speculation among mining geologists and mining men in general as to the relative merits of gravity methods in iron-ore exploration. Most of the investigations which have been carried out in recent years have been done by mining companies, and few if any of the results have been published. Three gravity surveys have been made in the Iron River-Crystal Falls area,&apos; " one by the U. S. Bureau of Mines, with inconclusive results, and the other two by Radar Exploration Co. for the Cleveland-Cliffs and the M. A. Hanna companies, with results not known to the writers. Both the last-mentioned surveys were detailed investigations, the stations being spaced as close as 10 ft along traverses,&apos; and were made to determine the feasibility of locating iron ore by gravitational methods. Because of the presence of a large body of ore already extensively drilled, Dr. Harold L. James of the U. S. Geological Survey, Iron River, Mich., suggested that a further test of gravitational methods of exploration be made in the Round Lake area of Iron County, see Figs. 1 and 2. This survey indicated a considerable regional gradient and led to a study of the surrounding gravity field and its relation to the major structural features of the syncline within which the iron formation lies. The southwestern part of Iron County presents a series of hills and hollows elongated in a roughly north-south direction. The bedrock topography is of pre-glacial origin. Relief is moderate; a maximum elevation difference of approximately 350 ft was observed during the survey. Major drainage is dendritic with the larger streams: the Brule to the south, the Paint to the north, and the Iron in the central part. Hills are thickly grown with hard- woods, and lowland areas, not under cultivation, are usually covered by second-growth softwoods. The area covered in this paper includes the southern half of Iron County, Mich., with a deep synclinal basin occupying the central part of the area, and the southeast corner of Gogebic County, immediately to the west of Iron County. The upper Huronian iron formation, slates, and graywackes which form the synclinal basin rest upon a greenstone basement. The basin has not been completely outlined by exposures, drill records or other means, as outcrops are scarce and the thick mantle of glacial drift makes geological investigations extremely difficult. Glacial drift varies in depth up to 300 ft or more. The drift is usually thickest under the hills and is thinnest in the depressions and along drainage courses where most of the bedrock exposures occur. The area over which gravity investigations were made is almost, entirely covered by glacial material. Bedrock of the basin consists of a complexly folded series of iron formation, slates, and graywackes. One of the series of slates has a high magnetic susceptibility due to the fine-grained magnetite it contains. This formation can be detected readily. by magnetic methods and provides a marker horizon which can be easily followed. The magnetic slates are stratigraphically above the iron formation, and much of the geological interpretation of the area is based upon the magnetic anomalies they produce.

Jan 1, 1953

By John V. Morgan

Although the Lansing-Kansas City groups One one of the more important producing horizons of Central Kansas, exploitation has been hindered by inability to consistently identify and correlate the various productive intervals. A study of gamma ray-neutron logs and core data indicates that definite zones exist which are related to production and which may be generally correlated over an appreciable portion of Central Kansas. A suggested system of zoning and nomenclature is developed and illustrated, along with examples of its specific application in overall evaluation and in development of zonal production characteristics. General adoption of the suggested system should aid appreciably in the future development of commercial Lansing-Kansas City production in Central Kansas. It is probable that similar systems might be developed for other regions where production is obtained from various uncorrelated and unnamed zones in thick pay intervals. GENERALIZED GEOLOGY OF CENTRAL KANSAS The most important large subsurface feature in Central Kansas regarding oil production is the Barton Arch, which is part of the Central Kansas uplift. The Barton Arch is a buried ridge of Pre-Cambrian granite running northwest-southeast, near which the majority of Central Kansas oil fields have been found. To the northeast of this arch, the granite dips sharply into the Salina Basin and similar basin areas to the west and south are termed the Hugoton Embayment and Anadarko Basin, respectively. This report deals Primarily with the region of the Central Kansas Uplift and its southwestern flank. Fig. 1 indicates the general location of subsurface structural features along with the oil and gas fields of central Kansas. Above basal granite lies the Cambro-Ordovician Arbuckle Dolomite which is the principal oil producing zone in Central Kansas. This formation, as well as those higher in the section, reflects the general underlying granite structure; however, the Arbuckle top is an erosional surface and most oil producing structures are probably topographic hills. Formations above the Arbuckle in ascending order may include those of the Ordovician, Silurian, Devonian, Mississippian, Pennsylvanian, and Permian periods as well as certain recent sediments. As the Barton Arch is approached, those formations below the Pennsylvanian and above the Arbuckle tend to pinch out until Pennsylvanian rocks, which include the Lansing-Kansas City groups, rest directly upon the Arbuckle. The Arbuckle itself is also completely eroded away at points on the Arch, but is up to 600 ft thick only 20 to 30 miles down dip. Formations of the Pennsylvanian system vary considerably in thickness but probably average about 1,000 ft as an overall total. The more commonly known oil productive zones are the Tarkio, Topeka, Toronto (Dodge), Lansing-Kansas City and Marmaton. Of these, the Lansing-Kansas City, which varies from about 200 ft to 400 ft in thickness, is the most important, since its areal frequency of oil production is exceeded only by that of the Arbuckle. Most Pennsylvanian rocks in Central Kansas were deposited in shallow seas which alternately covered, then retreated from the land. This resulted in recurring cycles of thin beds which cover relatively large areas. Small surface deformations during the period of deposition also caused variations in the type material deposited and its thickness. The local structures of Pennsylvanian time probahlv influenced the accumulation of

Jan 1, 1952

By O. J. C. Runnalls, L. M. Pidgeon

Some observations on the kinetics of the iodide process are reported. The deposition rate is geometry-sensitive in a system containing a finely divided titanium charge. Further, results indicate that the iodine diffusion rate influences the velocity of the process. The nonvolatile iodide, Til,, forms in the hot filament zone, thus removing iodine from the cycle. TITANIUM metal of 99.9 pct purity may be prepared using a refining technique originated by Van Arkel and de Boer.&apos; The purity of this metal, commonly called iodide titanium, exceeds that produced by any known process. In a recent application, the method was employed by Gonser et al.² to prepare titanium rods up to 2 to 3 cm in diam. In the Van Arkel-de Boer system, the relative influence of the fundamental mechanisms: l—production of titanium iodides, 2—gaseous countercurrent diffusion, and 3—decomposition, on the deposition rate have not been clearly established. Blocher and Campbell" have indicated that the controlling step in the process under practical conditions of operation may be the reaction rate of iodine with the crude metal. Fast&apos; reported that crude titanium metal reacted with iodine rapidly, even at room temperature, in his apparatus. Little has been reported on the effect of gaseous diffusion or decomposition on the deposition rate. It is these aspects of the process about which this investigation is centered. An attempt has been made to separate these latter effects from those due to the formation of the iodides at the crude metal surface by a division of the experimental program. Reaction of Iodine with Titanium Apparatus: In the investigation of gas-metal reactions of this type, the chemical reactivity of the halogen and halide vapors dictates the use of all-glass apparatus. In such a system standard techniques for measuring reaction rates are difficult to employ. Here, a simple apparatus was devised (Fig. 1) so that some indication of the reactivity of titanium powder with iodine vapor could be obtained. A stream of iodine gas was evolved from a bulb of controlled temperature and passed over a sample of titanium powder heated in a horizontal tube furnace. The product of the reaction, TiI4, volatilized and was condensed outside the furnace in a series of four glass bulbs, each cooled to room temperature in turn. Preliminary experiments indicated that distillation was retarded in a sealed evacuated system due to a pressure build-up in the condensing end of the apparatus. Hence, the system was pumped continuously using a mechanical pump and two oil diffusion pumps in series, through a liquid air trap. The iodine bulb was made large and a capillary restriction was inserted between the titanium bulb and the condensers so that the iodine pressure over the metal would approach the equilibrium pressure over solid iodine crystals. The effect of this restriction on the evaporation rate of TiI4, was determined separately. The iodine bulb was heated in an oil bath controlled to ±2°C. The titanium bulb temperature was automatically controlled to ±5°C. Procedure: About 200 mg of —30 mesh titanium powder, weighed to 0.1 mg, was placed in the reaction bulb after part B had been joined to part A. The powder was tapped into a long (5 cm) shallow mass along the bottom of the tube. Two chromel-alumel thermocouples were inserted into the magnesium radiator which was clamped to the reaction

Jan 1, 1953

By B. S. Lement

No appreciable stabilization of the austenite-martensite reaction occurs in a 15 pct Cr-0.7 pct C steel unless some martensite is initially present. Stabilization is induced by interrupting the subcool below M,; however, disappearance of the stabilization effect as manifest by burst formation of martensite may occur on continued holding at the final subzero reaction temperature. The higher the temperature of intermediate cycling after the initial subcool, the more permanent is the stabilization effect at the final reaction temperature. Appreciable conditioning of retained austenite occurs on reheating to about 500°C. These phenomena are explainable on the basis of the reaction-path theory. A RECENT investigation&apos; carried out by the authors has shown that isothermal transformation of austenite to martensite definitely takes place in a 15 pct Cr-0.7 pct C steel and that appreciable amounts of martensite can form in this fashion. Investigations2-" arried out on other steels and iron alloys make it seem probable that isothermal formation of martensite is a phenomenon of fairly general occurrence. The reaction-path theory of Cohen, Machlin, and Paranjpe5,7 explains isothermal transformation on the basis of thermal activation of strain embryos which generate martensite plates with a velocity approaching that of sound. On the other hand, the nucleation and growth theory of Fisher, Hollo-mon, and Turnbull8 egards isothermal transformation as due to growth of athermally formed martensite nuclei. The experimental evidence obtained thus far favors the reaction-path theory in that the martensite reaction seems to be nu-cleation-controlled rather than growth-controlled. Stabilization is another phenomenon of importance with respect to the austenite-martensite reaction. According to the reaction-path theory, stabilization is a result of relaxation of strain embryos. It is postulated that strain embryos are present at the austenitizing temperature in the form of dislocations or lattice imperfections in the austenite which vary in the extent to which the lattice is displaced along the strain reaction path leading to martensite. On quenching from the austenitizing temperature, athermal martensite starts to form as soon as the M. is reached, because the activation energy of the transformation which decreases with decreasing temperature is lowered to below the level of the highest energy strain embryos. Martensite plates are generated during the cooling below M, from embryos possessing energies above the activation energy corresponding to the temperature at which the cooling is stopped. The distribution of lower energy embryos is changed because of the elastic and plastic strains produced in the remaining austenite as a result of the transformation. This effectively increases the number of strain embryos at all levels of energy below the activation energy and tends to stimulate further martensite formation either iso-thermally or on subsequent cooling. However, if the temperature at which the cooling is stopped is high enough for relaxation of strain embryos to occur, some degree of stabilization against further transformation may be induced. Whether stabilization will be observed on subsequent cooling will depend on the extent of decrease of activation energy with temperature. If the activation energy decreases sharply with temperature, it is possible that transformation will appear to continue with decrease in temperature in spite of the loss of embryos by relaxation. However, with a more gradual decrease in activation energy, stabilization will be manifest by no further transformation on cooling over a measurable temperature range until the

Jan 1, 1954

By J. H. Hamilton, J. R. Lewis, J. H. Dismant, W. M. Fassell

RECENTLY this laboratory undertook the task of preparing some low carbon metallic cobalt by the carbon reduction of precipitated cobalt oxides. The oxides came in two lots and had the compositions given in Table I. Industrially, cobalt rondels&apos; are made by the carbon reduction of cobalt oxide in small reverberatory furnaces at temperatures near but not above 1050 °C. This is a slow and tedious small batch process but does give cobalt metal which is low in carbon (1 pct C). Inasmuch as these cobalt oxides were relatively low in copper and iron it was decided to reduce them with petroleum carbon in a small three-phase electric arc furnace of about 3 to 5 Ib of metal capacity. It was hoped such a procedure would save considerable time and perhaps also indicate an improved commercially feasible process. The furnace was preheated by using small pieces of carbon electrodes to maintain the arc until a temperature of 1500°C was reached. The broken pieces of electrodes were then removed and 500 g of the cobalt oxides and 60 to 100 g of petroleum coke added. At the end of the reduction reaction, a high lime flux was added to the furnace to facilitate the removal of sulphur. Due to the fineness of the cobalt oxide powder used and also to the presence of chlorides there was considerable dust lost in charging the furnace. This was overcome by preparing briquettes composed of the cobalt oxides, charcoal, and a little bentonite to serve as a binder. The results obtained are summarized in Table 11, which shows that the cobalt metal produced in the arc furnace was high in carbon varying from 2.5 to 3.5 pct. This, of course, is much too high. For certain uses, such as in the preparation of permanent magnets, the carbon content of cobalt must be low. It was necessary therefore to find an effective method of reducing the carbon content of the cobalt that had been prepared in the arc furnace. Van Arkel3 recommends the use of Co2O3 as a means of removing carbon from cobalt. Experiments by the authors indicate that carbon is removed with difficulty by this method. Other methods used, including lancing of the molten high carbon cobalt with a jet of oxygen, proved to be ineffective. The method finally used makes use of the fact that cobalt metal is decarburized by carbon dioxide at the temperature of the molten metal. Two methods were used: 1—carbon dioxide was bubbled up through the molten cobalt, and 2— molten cobalt was maintained in a carbon dioxide atmosphere. In the first method the gas was introduced below the surface of the molten metal by means of a quartz tube. A high frequency induction furnace was used to keep the cobalt molten in both of these experiments. This kept the metal somewhat agitated and no doubt was an important factor in hastening the decarburization &apos;process by the second method. Both methods gave satisfactory results as shown in Table 111. An interesting observation in connection with this &apos;work was that a small sample of carburized cobalt metal could be decarburized by heating it with an acetylene torch adjusted to give an oxidizing flame. This may have been due to the presence of carbon dioxide in the products of combustion. Samples of molten high carbon steel were decarburized by the same method and it is suggested that nickel and perhaps manganese can be decarburized in a similar manner. Additional work, including rate studies and other theoretical aspects of this problem, is in progress in this laboratory.

Jan 1, 1953

By Victor Formanek, Paul Chataignon, Maurice Rey

IT is found when floating oxidized lead ores by sulphidization, that the presence of calcium salts in the water, is usually detrimental and lowers the recovery. This effect is particularly marked in dry countries such as North Africa, where the waters often carry large amounts of calcium sulphate and where the ore may even contain gypsum. The effect of calcium salts is readily visible. Whereas in their absence cerussite is quickly stained brown and then black by sodium sulphide, in their presence the mineral remains very light in color. A similar effect is produced when barium sulphide is used as a sulphidizing agent instead of sodium sulphide. Magnesium salts have little or no effect and even tend to reduce the detrimental effect of calcium salts. A study of this phenomenon indicates that it is due to the precipitation of calcium or barium carbonate in contact with the mineral simultaneously with the formation of lead sulphide. The chemical reactions can be interpreted as: PbCO3 + Na2S = PbS + Na2CO3 CaSO4 + Na2CO3 = CaCO3 + Na2 SO4 They might also be written: PbCO3 + S = + Ca++ = PbS + CaCO3 The precipitation of calcium carbonate can be followed by the lowering of the pH with which it is accompanied. Magnesium carbonate is more soluble than calcium carbonate and usually does not precipitate under the conditions prevailing. It is interesting to note that calcium salts have no effect on anglesite (lead sulphate) because calcium sulphate is soluble, but barium salts hinder the sulphidization of anglesite because of the precipitation of barium sulphate. Remedies When calcium sulphate is present in large amounts, the softening of the water with soda ash is usually too expensive to be considered, but the precipitation of the objectionable calcium carbonate can be prevented in two different ways. One is the use of sodium hydrosulphide instead of sodium sulphide. This salt gives a lower pH than sodium sulphide and does not bring about the immediate precipitation of the calcium which remains in solution as calcium bicarbonate. The other procedure is to add ammonium salts such as the sulphate or chloride which have the property of increasing markedly the solubility of calcium carbonate. Ammonium salts have other effects such as cutting down conditioning time and accelerating flotation. They should be added to the flotation cells rather than to the ball mills. Table I. Effect of Sodium Hydrosulphide and/or Ammonium Sulphate on the Flotation of Two Oxidized Lead Ores Mibladen Ore4 La Plagne Ored Con- Tall- Con- Tail-centrate ing centrate ing Reagents Pb, Pct Pb, Pct Pb, Pct Pb, Pot Without addition of CaSO, NaS 56.0 0.68 43.4 0.65 NaSH 56.2 0.60 40.4 0.50 Na2S + (NH4)2SO4d 54.6 0.56 NaSH + (NH4)2SO4d 43.0 0.66 With addition of 40 lb/ton CaSO4 Na2S 39.4 3.85 34.0 3.21 NaSH 49.1 0.70 49.6 0.88 Na2S + (NH4)2SO4d 53.9 0.85 NaSH + (NH4)2SO4d 51.0 0.45 41.1 0.78 In table I are given the results of representative tests on two different oxidized ores. They show that the strongly detrimental effects of calcium sulphate can be offset by the two procedures outlined above. Sodium hydrosulphide is now used regularly on a mill scale on certain ores. Tests are being carried out with ammonium salts. It should be noted that malachite is subject to influences similar to cerussite. One final word of caution—when the ore is rich in primary slime, which is flocculated by the calcium salts, it may be indispensable to remove these by washing or precipitation with sodium carbonate instead of keeping them in solution by the above methods. Acknowledgment We wish to thank Socibtk Miniere & Metallurgique de Penarroya and Minerais et Metaux, for permission to publish these results.

Jan 1, 1951