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By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine' who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H'-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson'28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

By Rudolph G. Wuerker

Charles T. Holland (Head, Dept. of Mining Engineeri*, Virginia Polytechnical Inst., Blacksburg, Va.) Mr. Wuerker has presented a very interesting discussion of the use of triaxial test methods for investigating the strength properties of rocks. Such methods, no doubt, eventually will develop considerable information of interest to those concerned with the design of mine layouts, particularly in the field of pillar design. From his discussion of my recent article, "Cause and Occurrence of Coal Mine Bumps" (Holland Mining Engineering 1958, p. 933-1002), it is evident that in one place at least I did not make my meaning clear to him and perhaps others. To clear the matter up I think it best to quote from the article, somewhat more fully than did Mr. Wuerker, as follows: "4) In actual operations — because rocksare not perfectly elastic, homogeneous, nor isotropic and because local yield does occur — the maximum stress as demonstrated by Phillips (Ref. 22, pp. 64, 65) and indicated by much experience in mining, does not occur at the walls of the opening but at a short distance inside the pillar. Furthermore, the maximum stress does not reach as great a value as theoretical considerations and laboratory experimental methods indicate.* Actual distance inside the pillar, measured from the wall, at which the maximum stress exists, has not been determined. Observations in many mines, however, indicate that this distance could have a mini-value of one to six or eight times the bed thickness and that it is probably affected by width and height of the opening, depth of cover, and relative values of the elasticity and plasticity of materials comprising the roof, floor, and coal seam. The actual value of the stress produced probably lies between the theoretical maximum and the average stress concentration that would be produced if the weight of the strata above the unsupported opening were evenly distributed over the pillars for a distance equal to the opening width." The footnote reference in the above quotation referred to the following: "*For example, the Pocahontas No. 4 coal bed in southern West Virginia is mined under cover up to 1800 ft thick. Development openings are driven 18 to 20 ft wide, and the bed is about 6 ft thick. According to the work of Panek, the tangential wall stress at mid-bed height under these conditions would reach values between 4000 and 5000 psi. Actual tests of 3-in. cubes of this coal show its compressive strength would be much less than this, perhaps as low as 400 psi. Yet the pillars usually show no evidence of failure in these headings. In this same bed at a depth of 800 ft, the author has seen an opening 225 ft between supports lying between two old groves approximately 1100 ft apart. According to the theoretical considerations, the stress in the pillar walls would have been about 18,000 psi, yet the pillar showed little or no evidence of weight. In view of these observations, it is clear that the wall stress does not attain the maximum values indicated by theory." (Underlining added to original wording.) By referring to Fig. 2A of my paper it will be noted that theoretically the maximum pillar stress would occur at the pillar wall, i.e., at the passageway surface of the pillar. Obviously this cannot be correct in the cases of stress ranging from 4000 to 18000 psi since the coal at the surface of the pillar is under no constraint and cannot have a strength much greater than 400 or 500 psi. Hence, my conclusion that the maximum stress does not occur at the wall but back in the pillar some distance from the wall. Since these stresses are pushed back in the pillar from the wall, it is also obvious that the loads transferred to the pillar from the opening will be spread over a greater area and hence Pillar stresses will not rise to the values postulated by theory and photoelastic experiment. Further since to visual inspection the coal along the pillar wall did not appear to be failed the conclusion was reached that the stress shift was caused by local elastic or plastic yield and by difference in the elastic modulus of the rocks composing the mine floor, mine roof, and coal bed. Later on under the heading "Strength of Mine Pillars" (pages 1000-1002) the effects of constraint is briefly described. Also a formula taking into account constraint is developed relating pillar strength to the uniaxial strength of coal and the L/T ratio of the pillar. Since my paper was written, reports of experiments conducted in South Africa (Denkhaus, et. al., 1959), in Sweden (Hast 19581, and in Canada (McInnes, et.al., 1959) reveal that the conclusion expressed relative to the existence of a low stress area existing around the edges of pillars and solid faces as described above is generally correct. But it seems possible that where the wall stress developed is less than the unconfined strength of the rock composing the pillar and where the roof, floor, and pillar

Jan 1, 1961

By M. L. Leonardi

THE Searles Lake orebody is located in the north- west corner of San Bernardlno County. It is a dry lake bed with an exposed salt surface covering an area of 12 square miles. Recoverable mineral values are contained in the mother liquor below the surface of the lake. Stratification in the lake bed has separated the brine into two bodies which dlffer in composition. Although liquor is processed from both bodies, this paper will discuss only the upper structure brine. Fig. 1 illustrates a typical cross-section of the two commercial orebodies. The orebody is composed of a porous salt deposit 70 to 90 ft deep. The upper structure is separated from the lower orebody by a 12 to 16-ft thick impervious mud seam, as shown in Fig. 1. These salt structures are composed of 55 pct solid-phase salts and 45 pct voids which are filled with the original mother liquor. The brine wells are drilled to the separating mud seam and cased to wlthin 10 ft of the bottom. This is done to draw the brine horizontally from the bottom of the structure. It is pumped with multistage centrifugal pumps Into the plant at the rate of 3 milllon gal per day. The first process that was successful was developed by Charles P. Grimwood for the recovery of potash. The first evaporator unit was built in 1916. In the early twenties, Dr. Morse worked out a process for the recovery of borax. This made the cycle more efficient, as the end liquor could be sent back to the evaporators rather than being sewered. In 1926 the American Potash & Chemical Corp. was formed as a new company, and the entire plant was remodeled. The plant at that time produced only potash, borax, and boric acid. Since then the American Potash & Chemical Corp. has added processes for the production of USP boric acid, refined potash, sulphate of potash, soda ash, salt cake, lithium concentrates, Pyrobor (Na2B4O7) bromine, phosphoric acid, and lithium carbonate. The main plant cycle may be depicted as a closed cycle, see Fig. 2. The raw material, brine, enters the cycle to be mixed with the end liquor, known as ML2, from the pentahydrate borax crystallizers. The mixture of these two forms evaporator feed. Evaporator feed is pumped to the evaporators where it is concentrated, with respect to potash and borax. In the same operation water vapor, sodium chloride, salt trap salt, and clarifier salt are removed from the cycle, see Fig. 3 for potash plant product. The evaporators produce a concentrated liquor which contains approximately 19.5 pct KCI. This liquor is diluted as it enters the potash plant to keep all salts, except potash (KCI, 97.0 pct) in solution. Here the moist potash leaves the cycle at 100°F. The end liquor, known as ML1, is pumped to the borax pentahydrate crystallizers, where crude borax pentahydrate is crystallized and removed as solid phase. The ML2 is sent back to pan feed to be reconcen-trated, see page 207. Note that the only water to leave the cycle is in the form of vapor and moisture in the solid phase products crystallized. Thus there is a constantly cycling volume of liquor to which brine is added. Since the volume of liquor cycled does not increase, the brine is, in effect, evaporated to dryness. This would be true if there were no liquor losses. But, as in all processes, there are always unavoidable and accidental losses which reduce the volume of cycling liquors. The losses must be made up with brine. The concentration process is the beginning and the end of the cycling liquors. In this process there are three evaporator units of the triple effect counter-current type, that is, there are three pans in each unit and the heat flows in one direction while the liquor flows the other way through the evaporator pans, see Fig. 4. During the evaporation process a great deal of sodium chloride, burkeite, some sodium carbonate monohydrate, and a little lithium-sodium phosphate are crystallized. The volume of these salts is so great that they must be removed as they are formed or the process would come to a standstill. Brine and recycled mother liquor No. 2 enter the third effect evaporator pan from the evaporator feed storage tanks, see Fig. 5. A steady flow of liquor is removed from the bottom of the No. 3 pan and is pumped through the No. 3 cone of the salt trap, a clear liquor being returned to the NO. 3 pan. A portion of this clear liquor is pumped to the second effect pan. This process is repeated in each pan. The liquor from the No. 2 pan is pumped through the No. 2 salt trap cone and returned to the No. 2 pan.

Jan 1, 1955

By S. G. Proctor, D. L. Baaso, W. V. Conner

A double crucible system was developed for I-g scale plutonium reductions. The equipment consists of an inner MgO crucible, an outer MgO crucible, and a stainless steel pressure vessel. The reduction charge is PIaced in the inner crucible and the annulus between the inner and outer crucibles is filled with a mixture of calcium and iodine. The exothermic reaction between the calcium and iodine in the annulus supplies the heat required for complete reaction of the reduction charge ana' good metal coalescence. Metal yields of 80 to 85 ,pct were obtained from I-g scale reductions and yields as high as 97.5 pct were obtained from 0.5-g scale reductions. The system was used to reduce charges containing as little as 0.1 g of Pu resulting in metal yields up to 90 Pct. THIN metal foils of highly enriched plutonium isotopes are used as targets for cross section and other measurements. The isotopes are separated in the calutrons at Oak Ridge and are very expensive to prepare. Often, only 1 or 2 g of material are available thereby emphasizing the need for a method of preparing these small quantities of metal. Procedures for 1-g scale plutonium reductions have been described, but these procedures require elaborate or expensive equipment. For example, the procedure described by Anselin et al.1 requires an inert atmosphere glovebox and induction heating equipment. The procedure described by Baker2 also uses induction heating equipment to obtain the recommended heating rates and liner temperatures. Baker's procedure also requires high purity PuF4 with very little PuO2 present. The procedure described in this paper resulted from a search for a simple and inexpensive method for making 1-g scale plutonium reductions. EXPERIMENTAL Equipment. The equipment required for the double crucible system consists of a pressure vessel, two MgO crucibles, a MgO crucible lid, and a resistance-heated, vertical crucible furnace. The crucibles were slip cast from high purity MgO and were supplied by the Coors Porcelain Co. and the Norton Co. The pressure vessel and lid were fabricated from 316 stainless steel. Materials. The PuF4 used for this study was obtained from the P1utoniu:m Metal Production Department at Rocky Flats. The PuF4 was prepared in a con- tinuous hydrofluorinator by reacting Pu02 with HF at 650°C. The isotopic composition of the plutonium was approximately 93 pct 239PU, 6 pct 240PU, and 0.5 pct 241PU. Some of this PuF, contained less than 1 pct Pu02 (Batch No. 6 and 7), while other batches contained up to 15 pct Pu02 (Batch No. 3). The chemical analyses of all the PuF4 used for this study is given in Table I. The calcium was 99 pct pure, AEC grade, and only that fraction which would pass through a 20 mesh screen was used. The I2 was USP grade re-sublimed I2 which was ground before being used. Procedure. Various charge compositions and methods for loading the double crucible system were tested. The optimum conditions for 1-g scale reductions are described below. The double crucible system was loaded as shown in Fig. 1. The outer crucible was placed in the pressure vessel and the annulus between them was filled with MgO sand. The inner crucible was placed in the outer crucible, supported by a layer of MgO sand in the bottom of the outer crucible. A mixture of 5.2 g of Ca and 25 g of I2 was placed in the annulas between the two crucibles. The upper portion of the annulas was filled with MgO sand. Next, a layer of a mixture of calcium and I, equal to 20 wt pct of the calcium and I2 used in the main charge was placed in the bottom of the inner crucible. The PuF, to be reduced was mixed with a 30 pct excess of calcium and 1 mole of I2 per mole of Pu and this mixture was placed in the inner crucible. The charge was topped with a layer of a mixture of calcium and I2 equal to 20 wt pct of the calcium and I2 used in the main charge. The pressure vessel was sealed with a flat copper gasket and was purged by alternately evacuating and filling with argon. The purge valve was closed and the vessel was placed in a vertical crucible furnace which was preheated to 950°C. The furnace was turned off after 20 min of heating and the vessel allowed to cool. Experience has shown that. this amount of heating is sufficient to assure complete reaction of the charge. RESULTS AND DISCUSSION The double crucible system has been used to produce plutonium metal on a 0.1- to 1-g scale. Reduction

Jan 1, 1970

By J. C. Bierlein, R. A. Dodd

Endurance strengths at 10' cycles, fatigue-hardening rates, and endurance strength/0.2 pct proof stress ratios have been determined jbr a range of Cu(Ni), Cu(Si), and S.R.0. Cu(Au) solid solutions. Some douht is cast on simple cross slip models of fatigue hardening in view of opposite composition dependencies of hardening displayed by Cu(Si) and Cu(Au). The temperature dependencies of hardening also are the opposite of predictions made on the basis of a cross slip model. A correlation apparently exists between the fatigue strength/0.2 Pc~ proof s1.re.s~ ratios and rates of fatigue hardening. An increase in PS/PS due to alloying or temperature change is accompanied by a decrease in hardening rate, and vice versa. In recent years there has been much interest in the determination of the dislocation structure of fatigued metals and alloys. The accumulated evidence, e.g., Refs. 1 to 5, suggests that the structure may be dependent on the stacking fault energy, 7, of the fatigued metal in the same way that fatigue hardening rates have also been shown to apparently depend on u .6' 7 The above research followed the various earlier theories relating crack nucleation to ease of cross slip, e.g., Refs. 8 to 131 so "ggesting that y may indeed be the parameter of principal significance in all facets of the fatigue process. However, comparatively little attention has been paid to correlating engineering fatigue data with observations of the above type. Certainly, it would be useful if potential engineering fatigue performance could be assessed from a knowledge of easily determined alloy properties, and the present research originated from this standpoint. TO investigate the widest Possible range of 7 would require the use of two solvent bases, e.g., aluminum and copper, but a reasonable coverage can be provided by copper-based solutions alone. Therefore, it was decided to work with Cu(Ni) and Cu(Si) solid solutions, the approximate stackillg fault energies of which are given in Table I. The y range extends from low, Cu(7.5 at- Pet Si), to moderately high in Cu(2-5 at. ~ct ~i) and two of the Cu(Ni) alloys. The values listed in Table I should be regarded as qualitative only, being derived as follows. Dillamore and smallman14 quote a value of 85 i 30 erg.cm-2 for the stacking fault energy of pure copper, based on an earlier value due to Howie and swannl5 corrected by Brown's formula.'' Since the ratios (alloy)h(pure copper) have been reported17,18 for Cu(Ni) alloys containing up to 30 pct Ni, approximate ) values for these alloys can be computed, and a rough estimate of 7 for Cu(50 at. pct Ni) obtained by extrapolation. The relatively low y value obtained in this way for Cu(50 at. pct Ni) coincides with the observation of Nakajima19 that the stacking fault probability is a maximum at this composition. Likewise, the y values for the three ~u(~i) alloys are estimates based on values given by Swann and Nuttingo corrected on the basis Of Brown's estimate that the true 7 values are probably 2.3 times greater than those originally computed. In addition to the above alloys it was decided to investigate short-range ordered (s.R.O.) CU(AU) alloys containing up to 25 at. pct Au. This last alloy has been shown to have a well-defined planar arrangement of dislocations when deformed,21,22 probably due to cross slip being restricted by the S.R.O. Engineering fatigue data was to be represented by the determination of endurance strengths, and these were to be correlated with fatigue hardening and mechanical property data. EXPERIMENTAL I, order to study the desired properties and property changes, the following alloys were prepared: Cu(2.5 at. pct Si), Cu(5.0 at. pct Si), Cu(7.5 at. pct Si), Cu(5.0 at. pct Ni), Cu(25.0 at. pct Nil, Cu(50.0 at. pct Ni), Cu(5.0 at. pct AU), Cu(15.0 at. pct AU), Cu(25.0 at. pct AU). The copper and gold were zone-refined, while the silicon was semiconductor grade. The nickel was of 99.95 p,t. purity.* All alloys were induction-melted in a *Kindly supplied by the International Nickel co. helium atmosphere, appropriate precautions being taken to avoid segregation in the Cu-Au series. Rod stock was obtained by rolling and swag,ng. A few Bridgman single crystals were grown for fatigue-hardening studies, but most material was machined into polycrystalline fatigue speciments of the design shown in Fig. 1, and into polycrystalline tensile and fatigue-hardening specimens of simple cylindrical design. All specimens except Cu(Au) were annealed; the latter were quenched from above T, to produce short-range order. A few of the quenched alloys were examined for long-range order by step-scanning over

Jan 1, 1969

By M. O. Abo-el Fotoh, J. B. Mitchell, J. E. Dorn

The effect of strain rate and temperature on the tensile flow stress of a polycrystalline bcc alloy of magnesium containing 14 wt pct Li and 1.5 wt pct Al was investigated for strain rates of 3.13 x lom5 to 3.13 x 10-3 per sec over the range from 20° to 300°K. From about 180° to 300°K the alloy exhibited an ather-ma1 deformation behavior where the flow stress was independent of strain rate and increased only slightly with decreasing temperature. At lower temperatures the flow stress was strongly strain-rate- and temperature-dependent, characteristic of deformations controlled by thermally activated mechmzisms. The activation volume for thermally activated plastic defornzation was between 5 and 30 cu Burgers vectors, independent of plastic strain. This low-temperature thermally activated deformation behavior was found lo be in satisfactory agreement with the theoretical dictates of the Dorn-Rajnak1 formulation of the Peierls mechanism where deformation is controlled by the rate of nucleation of pairs of dislocation kinks over the Peierls energy barriers. SEVERAL studies of the low-temperature thermally activated deformation of bcc metals and alloys (molybdenum,1 tantalum,1 Fe-2 pct Mn,2 Fe-11 pct MO,3 and AgMg4) have revealed that the strain rate is controlled by the activation of dislocations over the Peierls-Nabarro energy hills. Although there is some uncertainty as to the nature and effect of solute atom-dislocation interactions during low-temperature deformation of bcc metals, it has been concluded by Dorn and Rajnak,1 Conrad,1 and Christian and Masters6 among others that overcoming the Peierls-Nabarro stress which arises from the variations in bond energies of atoms in the dislocation core as it is displaced is the probable mechanism controlling low-temperature deformation. The purpose of this research was to investigate the low-temperature plastic deformation of the bcc alloy Mg-14 wt pct Li-1.5 wt pct A1 to determine if the behavior of this alkali metal alloy might be analogous to that for other bcc metals. This alloy was selected because of its availability and its current industrial importance as a lightweight material for aircraft and aerospace applications. I) EXPERIMENTAL PROCEDURE Polycrystalline tensile specimens having cylindrical gage sections 2 in. long by 0.2 in. in diam were machined from as-received alloy sheet stock of Mg-14 wt pct Li-1.5 wt pct Al. Specimens were annealed in an argon atmosphere at 423°K for 4 hr and maintained in a kerosene bath together with the sheet stock to prevent corrosion. The resulting specimen microstructure consisted of a coarse uniform dispersion of incoherent precipitate MgLi2Al particles7 in a bcc 0 phase matrix having an average grain size of 150 p. Prior to testing the specimens were chemically polished in dilute hydrochloric acid. Comparison of tensile properties and microstructures of specimens cut from center and edge sections of the sheet stock revealed no effects of inhomogeneities in the sheet material. Tensile tests were performed on an Instron machine at crosshead speeds corresponding to tensile strain rates of 1.56 x 10-5 and 1.56 x 10"3 per sec. Stresses were determined to ±2 x 106 dynes per sq cm and strains to within ±0.0001. Average values of shear stress t and shear strain y reported were taken as one half the tensile stress and three halves the tensile strain, respectively. Flow stresses were taken at 0.05 pct strain offset. Test temperatures down to 77°K were obtained by immersing the specimens in constant-temperature baths. Lower-temperature tests were performed in a liquid helium cryostat to within ±2°K of the reported values. Prior to testing at the various temperatures and strain rates all specimens were prestrained at 2 35°K at a shear strain rate of 3.13 x 10-5 per sec to a stress level of 0.606 x 10' dynes per sq cm to obtain a uniform initial state. Additional tests were made to determine the effect of changes in strain rate and strain on the flow stress by rapidly changing the crosshead motion during testing. Shear moduli of elasticity, needed for analyses of the data, were obtained at several temperatures by a common technique of determining the resonant frequencies of vibrations of rectangular test specimens. 11) EXPERIMENTAL RESULTS Fig. 1 shows the experimentally determined flow stress vs temperature for two strain rates. Two distinct regions of behavior are evident. Below about 180°K the strong increase in flow stress with increased strain rate and decreasing temperature indicates that deformation is controlled by a thermally activated dislocation mechanism. At higher temperatures an athermal region is evident where the flow stress is independent of strain rate and only slightly dependent on temperature. The applied stress t to cause plastic flow was separated into two components:

Jan 1, 1969

By R. R. Judd, H. W. Paxton

The rate of dissolution of cementite was studied in three low-carbon materials: a zone-refined Fe-C alloy, an Fe-0.5pct Mn-C alloy, and a commercial low-carbon steel. The materials were spheroidized, ad then held isothermally at temperatures above the Al. The isothermal anneal was interrupted periodically by a water quench and the specimens were analyzed by quantitative metallography for the amount of aus-tenite formed during the anneal. The results of this study were compared with an analytical model for the process, which assumes that carbon diffusion in aus-tenite is the rate-controlling step for the cementite dissolution process. The correlation between the model and the experimental data is excellent for the zone-refined Fe-C alloys; however, the Fe-0.5 pct Mn-C alloys and the commercial steel deviate from the calculated model. This deviation is thought to be a result of manganese segregation between the carbide and the matrix. The rate of nucleation of austenite at carbide interfaces was reduced by the manganese addition and enhanced by the presence of ferrite-ferrite grain boundaries. PREVIOUS investigations of the nucleation and growth of austenite from ferrite-carbide aggregates are not entirely satisfying for at least one of several reasons. The most prevalent of these is a lack of quantitative data. Engineering studies have been run on many steels with little control over important parameters such as composition and initial aggregate structure. The data obtained are valid only for material with identical chemistry and thermal history. A more informative approach to the problem of aus-tenitization would be to determine the mechanism that controls the rate of solution of carbide in austenite and how it is modified by alloying elements. This information could then be used to calculate an austeniti-zation rate for any material, provided its composition and structure are known. The object of the present work is to establish the rate-controlling step for cementite dissolution in Fe-C austenite and to investigate the modification of this rate by small manganese additions. The composition and structure of the material used were carefully controlled and all measurements were designed to allow a quantitative analysis of the kinetic process that controls the austenitization rate. A MODEL FOR DISSOLUTION OF CEMENTITE Cementite dissolution has been analyzed mathematically by a model that approximates the material used in the experiments. This model postulates a regular ar-array of identical cementite spheroids with 4 C( diam, embedded in a grain boundary- free ferrite matrix. The analysis provides a detailed description of the dissolution of one carbide spheroid and a generalization of the solution by summation over all the carbides in the material. The carbides may be isolated by defining identical, space-filling cells of ferrite around them. If the cell dimensions are greater than the diameter of the austenite sphere resulting from complete dissolution of the carbide, and no interaction (through diffusion in ferrite) takes place between cells during the dissolution process, the model need concern only one cell, since the solution in each cell is identical. In the experimental material, the dimensions of the cell, the carbide, and the final austenite sphere are approximately 24, 4, and 8 p, respectively; use of the single cell is therefore justified. The experimental observations are made on the austenite nodules that form around each carbide during the dissolution process. The model concerns the growth of these austenite nodules. The attendant shrinking of the carbide can be obtained from the same analysis by an extension of the calculations. Several a priori assumptions are necessary to make the analysis of the growth problem tractable. They are: 1) carbon diffusion through the austenite nodule is the rate-controlling process; 2) local equilibrium exists at all interfaces, 3) the austenite nucleus that forms on each carbide instantaneously envelops the carbide; 4) during the austenite growth process, the diffusion flux of carbon in ferrite is insignificant; 5) a quasi-steady state exists in the austenite concentration field; that is, at any instant during the dissolution process, the austenite carbon concentration gradient closely approximates that for a steady-state solution; and 6) the effects of capillarity on the dissolution rate of the carbides can be neglected. Referring to Fig. 1, a mass balance at the y-a interface for an infinitesimal boundary movement gives: Where rb is the outer radius of the austenite shell, C1 and C are carbon concentrations at the interface in austenite and ferrite, respectively, see Fig. 2, is the diffusion coefficient of carbon in austenite for the concentration of carbon at the interface, and t is time. The fifth assumption permits the austenite carbon concentration to be approximated by the Laplace solution for the spherical case. Therefore, where C(Y) is the carbon concentration at r, and A and B are constants. Local interfacial equilibrium fixes the boundary conditions for the diffusion problem. They are:

Jan 1, 1969

By D. Cox, M. J. Duggin, L. Zwell

The carbides of approximate composition and Mn have been studied using X-ray diffraction techniques. Those carbides of the type (Fe,Aln)zC ave isostructural with cementite. The cell pararmeters a and c have minimum values at approximately 10 at. pd substitution of manganese for iron; no satisfactory explanation has yet been found for this phenomenon. The carbide fFeMn4)C has a monoclinic unit cell whose dimensions are close to those of ,11,15Cz A neu-troip-dij~ractiot~ study of (F'eAlrz4)C~ reveals that, like MnsCZ, it is isostructural with Pd5Bz. The iron and manganese atoms occupy the palladium atom sites, while the carbon atoms were found to have the same atomic coordinates as the hovon atoms. A neutrorr-diffraction study of indicates that the carbon-atom positions are very close to those occupied in (Fez.,ll/lr~,.3)C. In both carbides studied, tlre iron and manganese atomzs were found to be essentially randomly distributed, although, in the case of (Fe,.811fn1.2)C, it is possible that there may be a slight preference of manganese atoms for- the general (d) positions and a corresponding slight preference of iron atoms for the special (c) positions. It has been found that a complete range of solid solution exists between Fe3C and Mn3C at 1050°C,I although Mn3C becomes unstable when the temperature is reduced to 95O0C,' and can only be retained by rapid quenching. It is also known that a complete range of solid solution exists from Fe5Cz to M~SC~,~ although the stability range of carbides of the type (Fe,Mn)sCz as a function of the relative proportions of iron and manganese is not known. X-ray examinations of Oh-man's carbide3 and Spiegeleisenkristall,~ which have the approximate compositions (Fe3.67Mnl.33)C2 and (Fe3-,Mn,)C, where x lies between 0.4 and 1, respectively, have been made. The following carbides have also been studied: ] The lattice parameters determined during these investigations are listed in Table I. It is seen that carbides of the type (Fe,Mn)sCz have a monoclinic unit cell while carbides of the type (Fe,Mn)3C have an orthorhombic unit cell. It is evident that the variation of lattice parameters with manganese content is not linear for carbides of the type (Fe,Mn)3C. The coordinates of the atoms in (Fe2.7Mno.3)C have recently been determined by single-crystal analysis., The fractional atomic coordinates have been shown by Fasiska and jeffrey to be in good agreement withj those deduced from an earlier analysis of Fe3C by Lipson and etch.' However, it was impossible to determine whether iron and manganese atoms occupied ordered positions because of the small difference between the atomic scattering factors of iron and manganese. The atomic positions in Mn5Cz (Refs. 8 and 9) and Fe5C2 (Refs. 7 and 8) have been obtained only by comparisons made with the isostructural compounds P~SB~.' Since X-ray diffraction techniques were used in these investigations, accurate positioning of the carbon atoms, which have a low atomic scattering factor, was difficult. No attempt has been made to determine the atomic positions in the other carbides previously studied. It was felt that an investigation of the lattice parameters of a number of intermediate carbides of the types (Fe,Mn)sCZ and (Fe,Mn)& would be of interest. It seemed likely that a neutron-diffract ion study of such carbides would indicate whether ordering occurred between the iron and manganese atoms because of the large difference between the neutron-scattering cross sections of iron and manganese. It also seemed probable that such an investigation would provide a determination of the atomic coordinates of the carbon atoms. I) EXPERIMENTAL DETAILS Specimens, each weighing approximately 20 g, were carefully prepared according to the following proportions: The components were 500-mesh powders of 99.995 pct purity iron and spectroscopically pure carbon and a 200-mesh powder of 99.995 pct purity manganese. The component powders were intimately mixed by prolonged shaking, then each specimen was inserted into a spot-welded cylindrical container of tantalum foil, whose end was closed but not sealed. Each specimen in its envelope was then sintered at 1050° C for 24 hr in a thin-walled evacuated quartz capsule, such a time having been previously found sufficient for equilibrium to be attained.' Each specimen was then quenched in order to attempt to retain the high-temperature phase, as the literature indicates that transformations may occur on cooling. Debye-Scherrer X-ray photographs were taken of each specimen using a 114.6-mm-diam camera, Fig. 1, patterns 2 to 6. The exposure time was 6 hr using filtered iron radiation at a tube voltage of 40 kv and a tube current of 12 ma.

Jan 1, 1967

By Frank Harwood Riddle

Products made from the ores of the sillimanite group, and synthetic substitutes for them, have unique properties, and service tests prove that they are playing, and will continue to play, a major part in improvements in metallurgical processes. Also, they are examples of how comparatively useless, rare, or "museum" minerals have been made available in commercial quantities. Until research developed uses for them, the minerals had been observed only in small, scattered masses, or crystals. Improvements in ceramic processes and compositions have come about very gradually. In the last 10 or 15 years, several outstanding developments have been made. Of greatest interest to the mining and metallurgical engineers are those affecting the composition, necessitating the mining of new minerals, and improvements in ceramic products used in metallurgical processes. Sillimanite and Mullite Sillimanite (Al2O3.SiO2), then known as Fibrolite, according to Dana,' was first reported in 1792. In 1796, cyanite (Al2O3.SiO2) was first described.2 In 1873, Behrens published results of his microscopic study8 of porcelain. He showed that it contained what appeared to be crystals, which dissolved less readily than quartz and glass in hydrofluoric acid. Hussak4 described the presence of needlelike crystals as occurring in some instances in small amounts in certain porcelains. In 1908, Plenske and Zoellner both studied porcelain structure.5 Plenske observed that "sillimanite" might be present in masses of exceedingly minute grains which apparently were amorphous. Zoellner advanced the theory that the needlelike crystals were formed by a molecular change in the clay,

Jan 1, 1932

By K. B. Nowels

The attainment of efficient flooding to a large extent depends upon a knowledge of fluid movement through porous media and the pressures used in controlling this movement. Little has been understood con-cerning the fundamental principles involved in the forced drive of water-flooding and an attempt will be made to present some data which may be of interest. Considerable data and technical information pertaining to natural and artificial water-flooding have been presented in the past by Torrey, Umpleby, Fettke, Panyity and others. Their papers have thoroughly covered the description of past and present-day methods of oil recovery by flooding in the Bradford field, especially an article by Torreyl in the Petroleum Engineering Handbook. A bibliography of papers devoted to watcr-flooding, published in Mr. Torrey's article, is appended to this paper. No attempt has been made, therefore, to describe the installations and procedure necessary in flooding, thus permitting the writer to deal exclusively with the mechanics of water movement in flooding operations and its relationship to well spacing. Artificial water-flooding will probably always be the most successful in oil fields described by Herold as being under "capillary control"" and will probably be useless in fields naturally under hydraulic or volumetric control. The natural water drive in an oil field under either of these two controls may give efficient recoveries, as a result of the regulated encroachment of edge water. Such a "natural flood" resulting from the influence of edge water must not be confused with the term as used in this paper, however. Any reference to "natural flood" will here refer to the old method of flooding formerly used in the Bradford field. This was discovered largely by accident and utilized the hydrostatic pressure created by a column of water standing in a watered-out oil well in forcing the oil to an adjacent producing well. The same principles are involved in either natural or artificial flooding, and the latter method simply

Jan 1, 1933

By P. A. Beck, S. Kohara, M. N. Parthasarathi

IT has been shown1,3 that many observed phenomena related to annealing textures in f.c.c. metals can be adequately accounted for, at least in a qualitative way, by considering the orientation dependence of the boundary mobility, without any hypotheses concerning preferred orientation of nuclei. It was noted1 that this approach is particularly successful in the common cases of primary recrystallization in highly cold-worked polycrys-talline metals, where nuclei occur in great abundance, and that in the other extreme case, where the number of nuclei is very limited, or even only a single crystal is grown, the orientation dependence of boundary mobility has only a small effect, or none at all, on the orientations resulting from annealing. Recently Dunn described examples3-6 where observed secondary recrystallization textures apparently cannot be accounted for on the basis of oriented growth alone, but also require oriented nuclei, or at least the absence of nuclei in certain orientation ranges. In general, the great difficulty in correlating the preferred orientation of recrystallized grains with that of nuclei is inherent in the fact that nuclei are by nature very small, and that they are usually identifiable as "nuclei" only after growth, i.e., after they have already been subject to growth selectivity. An investigation was carried out by Liebmann and Lücke,' and also a very similar one by Graham and Cahn,' to obtain quantitative information on the orientation depend- ence of boundary migration rates in the recrystallization of slightly deformed aluminum single-crystal rods or plates, in which artificially nucleated recrystallized grains of predetermined orientation were grown. Liebmann and Lücke foupd maximum boundary mobility for boundaries across which the misorientation corresponded to a rotation of 40 deg around a common [Ill] axis, in accordance with earlier conclusions.9,1 Also, they confirmed that such an orientation relationship predominates among crystals growing into slightly extended single crystals from presumably random artificial nuclei. On the other hand, Graham and Cahn found no preferred orientation among crystals grown in a similar manner. It is not as yet known how these observations may be reconciled with each other. The view has been expressed in various papers5'10,21 that selective growth based on the orientation dependence of boundary mobility is not in itself sufficient to account for the formation of sharp re-crystallization textures, such as those often observed in highly deformed polycrystalline metals after annealing. The present work was undertaken to ascertain whether or not it is possible to obtain a sharp re-crystallization texture in a case where random nuclei are assuredly present in large numbers. It was previously found1' that high-purity aluminum crystals rolled 80 pct on the (110) plane in the [1T2] direction, when suitable precautions are taken, may be annealed for periods of about 1000 sec at 350°C without recrystallization. It was also found that the reluctance to recrystallize in this case is due to the scarcity of material in sufficiently deviating orientations to serve as nuclei. By using such a matrix,

Jan 1, 1959

By Alexander R. Troiano, Taylor Lyman

Studies of the transformation of aus-tenite at constant subcritical temperatures have been numerous since the work of Davenport and Rain.' Considerable information has been obtained on low-alloy steels and on high-carbon alloys containing undissolved carbide or graphite at the austenitizing temperature. Little is known of the isothermal transformation of aus-tenite containing in solution large amounts of both carbon and a single alloying element. In this investigation four steels containing one per cent carbon and with chromium in the range 3 to 9 per cent have been examined with the view to establishing the fundamental character of the isothermal reactions when all carbon and chromium are initially in solution in austenite. Experimental Procedure Alloys The chemical compositions of the steels investigated are given in Table I. The 4 per cent Cr alloy is a commercial steel. The other steels were made by the Carpenter Steel Co. as 50-lb., induction-furnace heats and rolled to 5/8 -in. round bars. Bars were softened at 650' to 700°C. before the specimens were cut. Most of the lines on the transformation diagrams presented here have been placed on the basis of the microscopic examinatioll of partially reacted specimens, Thees specimens were approximately 1/2 by 1/4 by 1/8 in. ill size, specimens of the 9 per cent cr steel were held 10 to 12 hr, at 1200°to 1225°C. before quenching to the various subcritical temperatures. The other steels were held for 2 to 2 1/2 hr. at 12ooOC. before quenching. These treatments, carried out in an atmosphere of purified nitrogen, produced an austenite grain size larger than A.S.T.M. So. I, some grains being 1 to 2 mm. in diameter. There were a few undissolved carbide particles in some specimens of the 9 per cent Cr steel. It is believed, however, that any errors in the results due to incomplete solution of carbon and chromium in austenite are negligible; that is, austenite compositions may be considered as being those listed ill Table I. X-ray Methods Constituents were identified and mar-tensite axial ratios determined from Debye

Jan 1, 1945

By L. G. Huntley

In view of the recent advance made in the knowledge of the nature and conditions accompanying the occurrence of oil and gas, and of the recent activity in drilling in Wyoming, Montana, and western Canada, a discussion of the probabilities of obtaining production in such a reservoir as the Dakota sand in general, and in particular districts, is thought by the author to be timely and likely to result in more intelligent operating in certain parts of the territory underlain by this sand. In Canada particularly it is thought that these general considerations have equal if not more significance in a consideration of the oil and gas possibilities of the formations than have the various local conditions. Age and Nature of Deposition of the Dakota Sand The Dakota is distinctive in that it is known to form a generally continuous sheet of sand underlying the greater part of Alberta, Saskatchewan, Manitoba, North and South Dakota, Montana, and large areas in Nebraska, Colorado, and Wyoming. It does not seem to have been laid down in more or less isolated lenses, as has been the case with most oil-sand horizons. Except in northern Alberta, the Dakota sand contains fresh-water fauna, having been deposited very uniformly over these wide areas in shallow water with prevailing strong currents. In northern Alberta marine and brackish water conditions prevailed. In this district it forms the basal member of the Cretaceous sediments, directly overlying beds of Devonian limestone along a great unconformity in the Athabasca River valley and eastward. In southern and western Alberta it is underlain unconformably by the Kootenay shales (Lower Cretaceous), and by Jurassic and Carboniferous rocks. In the United States in South Dakota it was in places deposited upon Cambrian quartzites, and in other places directly upon the granite. In the State of Dakota, and in the

Jan 1, 1916

By A. H. Larson, L. G. Twidwell

The influence which Au, Ag, Sb, Bi, Sn, and Cu have, both individually and collectively, on the activity coefficient of sulfur in liquid lead at 600"C zuas studied by circulating a H2S-Hz gas wlixture over a specific lead alloy until equilibrium was attained. Subsequently, the H2S concentration in the equilibrium gas mixture and sulfur concentration in the condensed phase were deterruined. The elements gold, silver, and antinzony (above 8 at. pct) increased the activity coefficient of sulfur. Bismuth had no apparent effect. Tin (above 3 at. pct) and copper decreased the coefficient. The influence of an individual element, i, on sulfur is best reported as the interaction parameter, riS, which is defined as The values o these first-order interaction zus are: ESzu = —55.0. These interaction parameters are used to predict the activity coefficient of sulfur in six fouv-component alloys and one seven-component alloy. Comparisons are made with direct experimental determinations. INTERACTIONS in dilute solution have been studied by many investigators. Most of the experimental work has been confined to solute-solvent interactions in simple binary systems and solute-solute interactions in ternary systems. Dealy and pehlke"~ have summarized the available literature on activity coefficients at infinite dilution in nonferrous binary alloys and have calculated from published data the values for interaction parameters in dilute nonferrous alloys. Interaction parameters are a convenient means of summarizing the effect of one solute species on another in a given solvent. Only a few investigators have studied interactions of the nonmetallic element sulfur in a metallic solvent. They are as follows: Rosenqvist,~ sulfur in silver; Rosenqvist and Cox,4 sulfur in steel; chipman, sulfur in alloy steels; Alcock and Richardson,% ulfur in copper alloys; Cheng and Alcock,' sulfur in iron, cobalt, and nickel; Cheng and ~lcock,' sulfur in lead and tin. The only reported work on the Pb-S system in the dilute-solution region is that of Cheng and Alcock.' Their investigation involved a study of the solubility of sulfur in liquid lead over the temperature range 500" to 680°C. The results may be summarized by the following relationship: S (dissolved in lead) + Pb(1) = PbS(s) log at. %S = -3388/T + 3.511 Experimentally, it was found that Henry's law was valid up to the solubility limit of sulfur in lead, i.e., at 600°C up to 0.43 pct. Their investigation did not include the study of sulfur in lead alloys. More accurate calculations could be made in smelting and refining systems if activity coefficients of solute species could be accurately predicted in complex solutions. One of the objectives of this study was to compare the experimental data with the values calculated from the equations derived from models for dilute solutions proposed by wagner9 and Alcock and Richardson. A temperature of 600°C was chosen as the experimental temperature to attain reasonable reaction rates and to minimize volatilization of the condensed phase. EXPERIMENTAL Materials. The Pb, Au, Ag, Sb, Bi, Sn, and Cu used for preparation of the alloys were American Smelting and Refining Co. research-grade materials. All were 99.999+ pct purity except the antimony and tin which were 99.99+ pct. The initial alloys prepared for this study consisted of twenty-one binary alloys, eleven ternary alloys, and one six-component alloy. The constituent elements were mixed for each desired alloy and were placed in a crucible machined from spectrographically pure graphite. The crucible was placed in a vycor tube which was evacuated with a vacuum pump and gettered by titanium sponge at 800°C for 8 to 12 hr. After the gettering was completed, the chamber containing the titanium was sealed and removed. The remaining sample chamber was placed in a tube furnace at 800°C for 2 hr and quenched in cold water. The final operation consisted of homogenization of the alloy for 1 to 2 weeks at a temperature just below the solidus for the individual system. The resulting master alloys were sectioned into small pieces and a random choice made for individual equilibrations. Cobalt sulfide (Cogs8) used to control the gas atmosphere in the circulation system was prepared by passing dried HzS for 24 hr over a Co-S mixture heated to 700°C in a tube furnace. This material was then mixed with cobalt metal to give a two-phase mixture which, when heated in hydrogen to a particular temperature, produced a desired H2S/H2 gas atmosphere in the circulation system. A Cu2S-Cu mixture also used in this study was prepared in a comparable manner. Apparatus for Equilibrium Measurements. The experimental technique of this study required apparatus

Jan 1, 1967

By H. T. Matson, G. Allan Wallis

In the Northern Rhodesia copper fields the size of the orebodies and the exceptionally consistent values over great distances made it possible to outline the ore with drill holes spaced at 1000-ft. intervals; in some cases, 2000-ft. intervals. Owing to the fact that the size of the deposits made it very evident that much outside capital would have to be called in to develop them and, owing to the wide spacing of the holes, it was essential that the sampling of drill holes be as accurate as possible, so that outside examining engineers could adopt the results as trustworthy within the limits of accuracy of the drilling method. With this object in view, the field staffs of the Selection Trust group of companies have studied for the past three years, and are still studying, drill sampling in a very thorough manner, and for this reason it is felt that these notes may be of interest to engineers or students who are, or in the future may be, in charge of drilling operations. The orebodies in this field lie in shales and sandstones, more or less indurated, in the lower strata of the Roan series, and the copper mineralization is in the form of sulfides predominantly, with some oxidized copper minerals. These interested in the geology and history of the area can find full details in a recent paper by Anton Gray and Russell J. Parker.' In some formations core recovery was good—between 90 and 100 per cent.—and where any difficulty occurred in recovering sludge, as in fissured ground, this was not insisted upon; but the samplers' difficulties, both practical and theoretical, do not commence until core recovery drops and sludge recovery becomes important, for if core is being ground up it is recoverable only as sludge, and naturally the sludge sample, which theoretically should contain only the material cut from the annular ring around the core, is being salted, in a sense, by the ground-up core. In the perfect core, where 100 per cent. core is recovered as well as 100 per cent. sludge, the two samples can be treated separately, as in the case

Jan 1, 1931

By T. E. Davidson, A. P. Lee

It is known from the early work of Bridgman that the two lowest-pressure transitions (I-II and II-III) are accompanied by substantial and abrupt changes in resistivity and Volume. However, unlike the temperature -induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of the pressure-in&ced transitions. This current work involves an examination of the structural and transformation characteristics of the bismuth I-II and II-III transitions under hydrostatic pressures. The relationship of initial structure to the transformation pressure, rate, resistivity change, and resultant structure is discussed. It is shown that the transition pressure and transformation rate are independent of the presence of grain boundaries and associated anisotropy-induced deformation. An observed hysteresis in both the I-II and II-III transitions is shown. BISMUTH is one of the most interesting of the elements exhibiting pressure-induced polymorphs since it undergoes several allotropic transformations at pressures below 90,000 atm. It is known from the early work of bridman1,2 that the two lowest-pressure transitions (1-11 and 11-111) are accompanied by substantial and abrupt changes in resistance and volume. However, unlike the temperature-induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of these pressure-induced transitions. It is the purpose of this work to examine some of the structural and transformation characteristics of the bismuth 1-11 and 11-111 transitions under hydrostatic pressures. Another interesting characteristic of bismuth is that, in its polycrystalline form, hydrostatic pressures of sufficient magnitude will induce severe progressive plastic deformation in the region of the grain boundaries.3 This deformation, which has also been observed in several other metals, is attributed to the high degree of anisotropy in the linear compressibility of bismuth, resulting in shear stresses in the grain boundaries when it is exposed to hydrostatic pressure. Most thermally induced allotropic transformations in metals, whether of the diffusionless ather-ma1 (martensitic) or isothermal nucleation and growth types, are dependent upon structure and prior history,4 viz., grain boundaries, deformation, and so forth. One logically wonders then whether the transformation characteristics of the pressure-induced polymorphs in bismuth might also depend upon initial structure, particularly with respect to the presence of grain boundaries and associated plastic deformation. In this investigation, the role of grain boundaries and plastic deformation on the characteristics of the bismuth I-II and 11-111 transitions will be established. The rather unique residual microstruc-tural changes associated with these transitions will be presented and discussed. The occurrence of a measurable hysteresis in both the I-II and 11-111 transitions will be demonstrated. The type of transformation mechanism based on the observed transformation rate will be discussed. EXPERIMENTAL PROCEDURE A) Apparatus. The hydrostatic pressure system utilized in this investigation is similar to that previously reported by Bridgman' and Birch and Robertson,5 and has been previously described.3 For the purpose of this work, the pressure medium utilized was a 1:l mixture of pentane and isopentane. Pressure measurement was by means of a manganin coil in conjunction with a Foxboro Recorder. The manganin coil was mounted in the bottom closure and inserted inside the pressure cavity. Based on calibration against a controlled clearance piston gage at approximately 10,000 atm, the estimated error in the pressure measurement was +2 pct. Assuming the nonlinearity in the pressure coefficient of resistivity between 10,000 and 28,000 atm to be not greater than 1 pct, then the estimated error in the range of the I-II and 11-111 transitions was +3 pct. B) specimen Material and Preparation. The bismuth utilized throughout this investigation was of

Jan 1, 1964

By David K. Hylbert

This study investigated roof falls in room-and-pillar drift coal mines in eastern Kentucky and utilized geologic methods for Predicting roof conditions in advance of mining. In the Highsplint mine, the roof was classified in four categories or conditions: Condition A and B (Laminated Shale); Condition C (Rolling Sandstone with Shale in Pockets); and Condition D (Zone of Major Sandstone Roll(s)). Structure contour and isopach maps of the Darby coal bed and associated immediate roof rocks were used to project axial trends of the sandstone roof. Trend mapping in the mine and on outcrop provided more detailed control for roof projections.

Jan 1, 1979

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By R. M. Goldhoff, H. J. Beattie

The high-temperature properties of a 1 Cr-Mo-V forging steel are described. A series of controlled heat treatments was designed to delineate the effects of austenitizing and tempering treatments, temile strength, and grain size on such properties. Studies indicate that the mechanical properties and their varlations under creep can be described by the initial metallurgical structures and their changes droPirzg exposure, particulavly the carbide reactions. Such structures are described and correlated with the mechanical properties. FOR many years the large steam turbine industry has relied on the 1 Cr-Mo-V type forging steel for critical applications. Because of its adequate heat resistance and relative economy, it is currently in use in the temperature range up to about 1050" to 1075°F. Attempts to understand the large property variations attainable in this steel involve the structural modifications due to the wide latitude in its heat treatment. The heat treatment essentially involves a two-step process which includes solution-ing of carbides in the austenite range followed by a suitable tempering treatment below the critical to adjust the level of properties. The latter step is referred to as "secondary hardening" and is basically an ordinary aging reaction involving carbides. In the commercial heat treatment of large components of such steel, homogenizing and stress-relief anneals may be included and have some importance in determining subsequent properties. Several studies of the engineering properties of this steel as a function of transformation micro-structure have been reported.1 3 However, in this steel the carbide reactions, which are a function of composition and heat treatment, appear to be the property-controlling factor rather than the micro-structure defined as a transformation product. Thus, the tempering resistance of this type of alloy steel is mainly a function of the size and distribution of alloy carbides.4 However, it is also necessary to consider the stability of the microstructure and the effect of dynamic carbide reactions on subsequent properties. It is the purpose of this paper to show the interdependence of properties and corresponding structures, particularly carbide reactions, developed for a limited set of controlled heat-treatment conditions applied to 1 Cr-Mo-V steel. MATERIALS AND PROCEDURE The material for this work came from a large production forging whose chemical composition is shown in Table I. The property data accumulated on this steel as a function of heat treatment were room-temperature tensile and smooth- and notch-bar creep rupture at 1050°F (notch geometry: shank diameter = 0.357 in., depth = 50 pct, radius = 0.005 in.). To achieve controlled structural variations the temperature and time of both austenitizing and tempering were varied in a manner to produce a series of eight steels each at one of two grain sizes and one of two hardness levels in proper combination for valid comparisons. This will be clear upon examination of Table I. Structural studies involved the use of optical and electron microscopy as well as X-ray and selected-area electron diffraction. To reveal the nature of carbide precipitations, electrolytic extraction techniques were used with subsequent analysis of the residue by X-ray diffraction. Weight losses of the steel specimens during electrolysis were measured and successive chemical fractionations of the residues were applied and checked by X-ray examination. The details of fine structural distributions, morphologies, and crystallography of the precipitates as well as dislocation distributions were investigated by examining in the electron microscope three common types of preparation. a) Relief Replicas. Mechanically polished sections were etched in 2 pct nital, replicated with a nitrocellulose film, which was shadowed by chromium vapor deposited at a glancing angle of 20 deg. b) Extraction Replicas. A thin film of carbon was vapor-deposited on the polished and etched surface. The carbon films were then etched off and gathered on electron-microscope supporting grids. The carbides left imbedded in the carbon replica in their original distribution were then examined crystallo-graphically by selected-area electron diffraction. c) Thin Films. Specimens were mechanically ground and polished down to a thickness of 0.001 to 0.003 in. Final thinning was done electrolytically in a "chrome-acetic" electrolyte. When holes began to appear in the foil, the voltage was interrupted and applied in several 1-sec bursts. Sections of the foil between holes were thin enough to pass a 100-kv electron beam that carries an image.

Jan 1, 1965

By H. T. Clark, H. K. Work

The instrument for the rapid determination of carbon in steel, described in this paper, was developed originally to facilitate the operation of the pilot-sized open-hearth furnace in the Jones & Laughlin Research and Eevelopment Laboratory. In this small furnace, with its shallow bath, the drop in carbon is accelerated, and a rapid, reliable test for carbon content is indispensable. This problem becomes rather acute when it is desired to finish heats at a carbon content higher than can be estimated with any degree of accuracy by the fracture test. Several independent methods for determining carbon were investigated, therefore, and it was found that a relatively simple magnetic device could be made to give reproducible results. A laboratory instrument was designed and set up for the use of the furnace operators. It was tested exhaustively in the laboratory and was used with considerable success for following the carbon content in the furnace bath. As soon as sufficient data had been compiled to indicate that the instrument might have a wider application, a more rugged model was constructed and placed in the mill to be tested on commercial heats. Finally, about a year ago, instruments were furnished to the plant open-hearth shops, and these have been in use since that time. As a matter of convenience, the instrument has been named the "Carbanalyzer," and will be referred to by this designation in the following pages. $ Eaklier Investigations While by far the greatest number of magnetic investigations in which the carbon content of ferromagnetic materials was considered have had to do with the evaluation of the magnetic properties of steels of known

Jan 1, 1940