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William Andrews Clark, former United States senator from Montana, died at his home in New York on March 2, at the age of 86, after a brief illness due to pneumonia. He was the last of the three great Montana mining magnates, Clark, Daly and Heinze. He was born in Connellsville, Pa., on Jan. 8, 1839, and in 1863 arrived in Bannock, Ida., with only five dollars, after a journey of 65 days. On reaching Idaho, he became successively a miner, teamster, machinist, railway builder, mine owner, capitalist and, in his more recent years, philanthropist and art collector.

Jan 1, 1925

By Lo-Ching Chang, Kenneth M. Goldman

INTRODUCTION THE kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was simple. A graphite crucible 1 5/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an induction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature [ ] for 3-5 min., after which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 min. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the temperature of the furnace in 1 to 1 1/ 2 min. Slag

Jan 1, 1948

By S. R. Goodman, Hsun Hu

A study has hem made of the formation of annealing textures in an 18-8 austenitic stainless steel (Type 304L) from various deformation textures obtained by rolling at different temperatures. When the deformation texture is a mixture of the ferritic type and the brass type owing to the pres -ence of both martensitic ferrite and retained aus-tenite in the specimen, recrystallization takes place by the growth of the existing austenite phase. In a previous report,' it was shown that the rolling texture of austenitic stainless steel (Type 304L) changed gradually from the brass type to the copper type with increasing temperature of deformation above 200°C. These changes are similar to those in high-purity silver2,3 and electrolytic copper;4 a brass-type texture is favored at low rolling temperatures, whereas a copper-type texture is favored During the course of rolling -texture transition from the brass type to the copper type, the subsequent recrystallization textures change accordingly. The orientation relationship between the annealing textures and the various rolling textures, being consistent with previous observations on various fcc metals, can be described as [Ill] rotations of approximately 25 to 40 deg. Carhide precipitation may influence the annealing textures. at high rolling temperatures. Furthermore, the annealing textures in high-purity silver5 and electrolytic copper4 were found to depend entirely on the prior deformation texture. From a copper-type rolling texture a strong cube texture will form upon recrystallization, whereas from a brass-type rolling texture the annealing texture will be quite different from the cube orientation. In an earlier comm~nication,6 the formation of a strong cube texture in 18-8 austenite stainless steels (Types 304 and 304L) was reported briefly by the authors. The present paper constitutes the results of a complete study of the annealing textures obtained from a

Jan 1, 1965

By Albert Sauveur

This paper explains the possibility of using advantageously a boiling solution of sodium picrate to reveal dendritic segregation in steel. The mechanism of the action of the reagent is described. The failure of manganese alone to produce persistent dendritic segregation is also considered. IRON, like other metals, solidifies through the formation of dendritic crystals; iron alloys forming solid solutions, like other solid solutions, solidify likewise through the formation of dendritic crystals. The alloying elements or impurities as well as the inclusions segregate generally in the interstices, or "fillings," between the axes and branches of the dendrites; that is, in the portions last to solidify. This results in dendritic segregation or heterogeneity, which is generally persistent and makes possible the revelation of the dendritic crystallization of the metal through the selective action of a suitable etching reagent.1 For this purpose, a cupric solution, such as Le Chatelier's, is generally used, copper being deposited on the pure, or relatively pure, ferrite present in the axes while the fillings remain free, or relatively free., from copper deposition. The dendritic structure, formed on solidification in a steel containing 0.50 per cent. carbon, 0.37 per cent. manganese, 0.12 per cent. silicon, 0.07 per cent. sulfur, and 0.035 per cent. phosphorus is shown, after treatment with Le Chatelier reagent, in Fig. 1 under a magnification of 8 diameters. Commercial steel always contains inclusions of manganese sulfide, which are located in the fillings of the dendrites. Comstock has shown that boiling sodium picrate imparts a dark coloration to these inclusions. We find that this reagent likewise reveals dendritic segregations in commercial steel, as shown in Fig. 2, under a magnification of 8 diameters, which represents the same spot as that shown in Fig. 1. The fillings

Jan 2, 1924

By Hiroshi Oikawa, A. G. Guy

Recent experimental evidence has shown that it is often incorrect to neglect the reactions occurring at an interface with respect to the diffusion reactions. By introducing reaction-rate constants and k for the transfer of components 1 and 2 between the a and b phases, a phenomenological description has been devised for the coupled processes of diffusion and in-terfacial reaction. An illustrative example has been analyzed with the aid of a suitable computer program. The results indicate that for kab values on the order of 10'1 cm per sec and Ð values of about 10¯10 sq cm per sec, the interfacial reactions are significant during the first 10 2 to l0 6 sec of a diffusion experiment. Among the observable effects of the interfacial reactions in this case appear to be the burying Kirkendall markers and an anomaly in the initial shifting of these markers. THE study of diffusion between two phases is especially important because of its direct connection to phase transformations. For example, the transformation of austenite to ferrite involves diffusion in the a and ý phases and also an interfacial reaction (trans formation) at the a/? interface. If ferrite and aus-tenite are the two members in a diffusion couple, the same two reactions occur during the diffusion process. The numerical values obtained for the diffusion coefficients and interfacial-reaction constants from diffusion experiments can then be employed to predict phase-transformation behavior. Refinement of the calculations of phase transformation is also suggested by the present method for treating two-phase diffusion. In the recent paper by Nolfi et al.' only the solute com ponent is considered in the interfacial reaction accompanying a phase transformation. The present analysis demonstrates that both components must be considered. It is generally recognized that reactions of some kind must occur at the interface in a two-phase diffusion couple, but usually it is assumed that the interface reaction occurs so rapidly that its effect on the overall process is unobservable because the slower diffusion process determines the kinetics of the process. However, Seith and Heumann 2 pointed out that effects of the interfacial reaction should always occur in the early stages of diffusion, and recently Eifert et al. 3 have shown that interfacial reactions influence the composition and motion of the interface in a/ß Al-Cu diffusion couples during the entire course of prolonged, high-temperature treatments. A general procedure for handling the combined processes of interfacial reaction and diffusion in a binary, two-phase system is to introduce kinetic coefficients for the interface reactions and to develop the system of equations governing the interlinked processes of diffusion and interface reaction. The resulting equations, although not amenable to solution in closed form, can be usefully manipulated by a digital computer. INTERFACIAL REACTIONS IN TWO-PHASE DIFFUSION Consider the general case of diffusion between two solid solutions, a and ß, which are adjacent phases in a binary system, Fig. 1. Two semiinfinite bars having compositions c1 and c0ß are jointed at x = 0. If concentrations are expressed in volume fraction,4

Jan 1, 1970

By H. Sigurdson, C. H. Moore

Extensive studies have been carried out on electric furnace and blast furnace slags obtained in the winning of iron from its ores. These slags normally consist of elements of the gangue minerals present in the ores, as well as the added flux materials. In consequence, melts of CaO, MgO, Al2O3 and SiO2 can be considered as representing typical slag compositions. When a slag of this composition cools, it usually crystallizes according to predictions possible from an equilibrium diagram of these constituents, providing the melt is not undercooled to form glass. The melt is either viscous or fluid, depending upon the ratio of binary cations to silica, and crystallizes easily or forms a glass for the same reasons. If the melt is not overheated so that carbides of the metal components of the slag are formed and if the composition of the slag is so adjusted that it has a high fluidity, liquid equilibrium is attained and the slag can be held in a liquid state for extended periods of time. Upon tapping, the slag crystallizes into minerals, the type and proportion of which are determined by the melt composition. Since equilibrium is attained, the holding period is not critical. In melts containing a large increment of titanium, however, the normal slag procedures are not applicable. Titanium, as one of the atomic transition elements, is, at elevated temperatures, capable of being reduced to form metalloid compounds much more readily than the refractory oxides present in normal slags. In consequence, an oxide melt containing titanium never reaches equilibrium in a reducing environment, but continues to shift its composition until cooled. If melts of this nature are cooled and samples submitted to metal-lographic and X ray analysis the course of reaction and crystallization in this type of slag can be determined. Preparation of Slag The slags investigated fell into the system CaO-MgO-TiO2-Al2O3-SiO2 and were produced from ilmenite ores reduced by carbon in an electric furnace. Since the equilibrium series1 and the laboratory smelting of ilmenite2 are described in two of the accompanying papers, detailed description of the smelting procedure is not required here. However, certain essentials must be mentioned. Two types of melts were used to produce slags studied in this investigation. The first series of smelts made to determine proper flux addition were produced in a 4 lb Ajax induction furnace. The charge, consisting of ore with the proper flux addition, was heated in a graphite crucible until fluid, held fluid for a sufficient time period to obtain 1-5 pct FeO content, and poured. Because of the small size of the charge only the final sample of these melts could be examined. In the melts made in the 50 lb arc furnace, however, grab samples taken at 10 min. intervals between time of initial melting and final pouring were available for examination. These samples allowed a much clearer picture of the course of reaction and crystallization. amounts of ferrous oxide and reduced titanium compounds is opaque to transmitted light. Therefore, all petro-graphic studies had to be made on polished slag sections. A representative sample of slag was cut or broken, mounted in a thermosetting plastic, ground flat using 400 grit silicon carbide, the coarse scratches removed with 600 grit silicon carbide and polished on billiard cloth using levigated alumina. Rouge was avoided because of the entrainment of the red particles in pores in the slag, causing a possible confusion with some of the mineral phases. In order to prevent sample projection above the plastic surface red bakelite was used to hold the sample, and backed up with clear lucite. In this manner sample labels could be permanently retained in the mounting. The polished samples were examined on a Bausch and Lomb metallograph at magnifications of 250 X, 500 X, 1000 X and 1800 X. The instrument was equipped for examination of specimens under bright field illumination and with crossed nicols. A magenta tint plate to aid in color tone differentiation was also used. Petrology of Slags In order to determine the composition and mineral relatinos of a previously unreported system petrologically, it is essential that the starting composition, reaction temperature and final composition be known. The chemical composition of the ilmenite ore used in these smelts is given in Table 1, and the complete analysis of a typical high titanium, low iron slag is given in Table 2. In the winning of TiO2 from ilmenite by a smelting process it is necessary to produce a slag which will melt at an economically feasible temperature, remain molten as the iron is removed by reduction, be fluid enough to be readily removed from the furnace, contain a high percentage of TiO2 and a low percentage of reduced titanium com-

Jan 1, 1950

By J. W. Spretnak, H. R. Ogden, A. G. Imgram

The effect of working reduction, stress-relief annealing, and recrystallized grain size on the tensile and notch-tensile properties of molybdenum and Mo-0.5 Ti was studied. It was found that increasing the amount of working reduction increased the strength and reduced the tendencies toward brittle behavior. Stress -relief annealing did not alter the strength but lowered the transition temperature. Increasing the recrystallized grain size lowered the strength and raised the transition temperature. The notch -unnotch strength ratio began to decrease with decreasing temperature at temperatures below those at which the notched ductility fell to zero for all of the micro structural conditions investigated. BEING bcc metals, the refractory metals in Groups Va and VIa (V, Cb, Ta, and Cr, Mo, W) undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures. Previous research has shown that molybdenum and tungsten not only have higher transition temperatures than columbium and tantalum but show a marked sensitivity of transition temperature to structure as well.' Recrystallized materials become brittle at considerably higher temperatures than is the case with material having a worked or fibered micro-structure. Evidence of structure sensitivity has also been detected in columbium- and tantalum-base alloys containing appreciable amounts of molybdenum or tungsten such as F-48 (Cb-15W-5Mo-1Zr) and Ta-10w.2 This paper describes the results of research conducted to further evaluate the effects of metal. lurgical structure on the low-temperature tensile and notch-tensile properties of molybdenum and Mo-0.5Ti. The effects of rolling reduction, stress-relief annealing temperature, and recrystallized grain size were studied. Considerable progress has been made in explaining the fundamental mechanisms of the flow and fracture characteristics of bcc metals. Several of these concepts are helpful in interpreting the data obtained in this study. Brittle fractures occur when the highly temperature-sensitive yield strength equals, or exceeds, the temperature-insensitive brittle cleavage fracture stress.3 The rapid increase in yield strength with decreasing temperature, characteristic of all bcc metals, is therefore of primary concern. petch4 has described the yield strength, ay, (stress required to initiate plastic flow) of bcc metals by the expression where ai is the frictional resistance to slip, Ky is a constant numerically equal to the slope of a a vs curve, and 2d is the average grain diamefer. The oi term itself is thought to be composed of a temperature-insensitive component dependent on impurity content and second-phase particles and a temperature-sensitive component dependent on the Pierls-Nabarro force.5 This equation has also been demonstrated to hold for the flow stress (stress required to maintain continued plastic flow).' Brittle-crack nucleation is thought to occur by the coalescence of dislocations piled up in slip planes at sessile dislocations or twin and grain boundaries.7,8 These proposed mechanisms require that a large number of dislocations be released into the active slip planes so that sufficiently large stress concentrations are produced at the dislocation pile-ups to enable coalescence into a micro-crack. Therefore, at least a microscopic amount of slip must occur in some grains to facilitate initial crack formation. Cottrell 7 has predicted that brittle fracture, nucleated by slip, should occur when where ty is the shear yield strength, ß = 1 in un- notched xension, u is the shear modulus, and y is the effective surface energy. This equation incorporates the Griffith concept of fracture that a crack will propagate if the decrease in strain energy equals or exceeds the increase in surface energy.

Jan 1, 1964

By H. P. Stuwe

It is investigated whether a model of sphere packing permits the computation of the lattice parameters and their variation with concentration in various a phases; it does, except in phases containing silicon. Several observations indicate that a particular role is played by the "E-atoms" in the lattice. THE phase is formed by many alloys of the transition elements.'-' Its structure has been described by Bergman and Shoemaker,5,8 Dickins, Douglas, and Taylor,7 and Kasper, Decker, and elanger.' There are five kinds of crystallographically equivalent positions for the 30 atoms in the unit cell which have been designated by these authors I, 11, 111, IV, and V or, in the same sequence, A, B, C,D, and E, as shown in Fig, 1. For the purposes of the present paper two elements of the lattice will be discussed separately: The lattice planes perpendicular to the c-axis which are made up by the atoms A, B, C, and D and which determine the a-parameter; and the close-packed "vertical rows" of E-atoms which determine the c-parameter. asper,9 and Frank and kasper10 described the a phase and other complex structures as sphere packings. In these papers particular attention is paid to the coordination polyhedra. Lattice positions with an equal number of nearest neighbors are considered equivalent regardless of their crystallo-graphic description. This seems to work very well for the explanation of ordering phenomena in the a phase as far as information on this is available." If the description of the phase as a sphere packing is valid it should be possible to draw two further conclusions: 1) It should be possible to calculate the lattice parameters from the atomic radii of the components, and 2) It should be possible to predict the variation of the lattice parameters with concentration within one phase field. Both points are discussed in this paper. PROCEDURE Measurements of lattice constants were done with a symmetrical back-reflection X-ray camera. With Cr-radiation, about a dozen a1 lines could be observed with most samples. From the (550/710)- and 720-lines the a-value was computed. With this value the c-parameter was calculated from the (333)- and (413)-lines. Finally, the position of all the other lines was computed from the lattice parameters thus obtained. In this way the validity of the indexing could be checked and, at the same time, this proce- dure gave an estimate of the accuracy of the lattice parameters. A correction was made for film shrinkage. The atomic radii used in the computations are the Goldschmidt radii for coordination number 12. Actually, some of the atoms have a coordination number of 14 or 15, but the error thereby introduced is small. * For the computation of lattice constants from the atomic radii an "average atomic radius" of all components was used, i.e., complete disorder was assumed. Although this seems to be true for some systems like OS-Cr,4 it is not true in others.11,13,14 The ordering model, however, which has been suggested by Kasper on the basis of extensive research lets both kinds of atoms contribute to both the ''vertical rows" and the lattice planes perpendicular to them, so that even with ordering of this kind the assumption of complete disorder cannot introduce a very serious error in calculating lattice parameters. RESULTS Bergman and shoemaker6 gave a table of the interatomic distances in the Fe-Cr phase. If we disre-

Jan 1, 1960

By Harry M. Mikami

Chromite is the only ore mineral of metallic chromium and chromium compounds and chemicals. Because of this fact, chromite and chrome ore are used synonymously in trade literature. In commercial market quotations, chrome ore is the term commonly used. Chromite per se, because of properties imparted by its chromium content, is used in refractories and in special purpose molding sands for metal casting. There are many other minerals containing some, generally minor, amounts of chromium, but none are commercial sources of the element (Thayer, 1956). Chromium and chromite have many diverse uses that, directly and indirectly, critically affect vast segments of our modern industrial system. Most important are probably the metallurgical applications wherein chromium is a component of heat-, abrasion-, corrosion-and oxidation-resistant and high-strength alloys of many types. Stainless steels are the largest volume category of chrome-bearing alloys. Chromium chemicals are used in leather tanning, in pigments, dyes and mordants, printing, chemical process industries, photography, pharmaceuticals, metal plating, pure chromium metal production, and for many other purposes. Chromite is a necessary constituent in basic refractories indispensable for the production of steel, copper, cement, and glass. Under present conditions, the US and North America, with the possible exception of Cuba, have no commercial ore reserves. There are chromite deposits, as will be described, but they would be used only under highly abnormal conditions if all outside sources were cut off for an extended period. All chromite used in the US is imported from the eastern hemisphere in which are contained the principal world reserves. The main suppliers in 1980 were the Republic of South Africa (43%), the USSR (21% ), the Philippines (12%), Albania (11 %), Turkey (8%), and others (5%). The strategic nature of chromite is obvious. End Uses-Grades and Specifications As noted before, the three principal uses for chromite are metallurgical, refractories, and chemical with a fourth minor use as foundry molding sand. For metallurgical applications chrome ore is first reduced in electric carbon arc furnaces to various types of ferrochromium alloys. There are high, medium, and low carbon ferrochromiums with carbon ranging from 0.01 up to 10%. Chromium itself ranges from 50 to 73 %. Ferrosilicon chromium and ferrochromium-silicon grades have chromium from 33 to 67% and silicon from 3 to about 48%. Since iron is reduced with chromium, the Cr:Fe ratio of the ore will determine the ultimate grade of the ferrochromium whereas carbon and silicon can be controlled during processing. MgO, A12O3, CaO, and excess SiO2, are removed in slag. A small amount of pure chromium metal is prepared by alumino-thermic and electrolytic processes from essentially iron-free chrome components that have been made via the chemical route. The higher grades of ferrochromium with chromium in the 66 to 73% range can only be made from ores with not only high chromium content, but low iron, i.e., high Cr:Fe ratio. These ores, conventionally termed metallurgical grade, have Cr2O3 contents of 45 to 56% with Cr: Fe ratios of 2.5 to 4.3. A standard composition is generally 48% Cr2O3 and 3:1 Cr:Fe ratio. Very high grade ores are often blended with lower grades even with the high iron chemical grade. For some ferrochromiums, additions of high alumina refractory grade are used as slag conditioners to facilitate smelting while still contributing chromium values. A lower grade ferrochromium, the high carbon charge chrome, has become the predominant grade in use today for making chromium-bearing steel alloys. This

Jan 1, 1983

By Sam N. Dewitt, Albert S. Trube

This paper presents a discussion of the pressure maintenance operations which were begun in the New Hope Field. Franklin County. Texas. in 1944. The project has required the injection of extraneous waters at depths from 7.300 to 8.000 ft with intake well-head pressures up to 4.000 psi in three different reservoirs — the Bacon. Hill. and Pittsburg. Records of oil and water production. water injection and the GOR have been kept for each reservoir and reservoir pressures were taken at regular intervals. These data indicate that the Bacon Reservoir had no apparent water encroachment up to the time of water injection. However. the Pittsburg and Hill reservoirs had some natural water influx hut not sufficient to prevent pressures from declining below the bubble point. The Bacon and Hill reservoirs responded almost immediately to water injection. while the Pittsburg which is the least permeable. has shown good pressure response only since .August, 1948. The principle objective of the project has been to increase ultimate recovery. Success of the project to date also has resulted in reduced lifting costs. Esti- mates based on the initial water breakthrough patterns indicate that the primary objective of substantial additional recovery will he accomplished, and there is a possibility that the original estimates elf oil recovery with pres-sure maintenance will he exceeded. INTRODUCTION This pressure maintenance project was one of the earliest primary pressure maintenance programs to he attempted on a multiple zone field. There are three producing reservoirs into which water is being injected for the purpose of maintaining pressure and increasing the ultimate recovery- from each. This paper is limited in scope to al1 account of the development of the project. the pressure production relationship prior to the injection of water and the effect of water injection on the producing reservoirs. Also discussed are the nature of the injection system and the indicated results on initial water break-through in the Bacon Reservoir. FIELD CONDITIONS The New Hope Field, which is located about 12 miles northeast of Winusboro, Franklin County, Texas, is an elongated symmetrical anticline containing four known oil reservoirs. The reservoirs are of the Trinity group of the Comanchean or Lower Cretaceous period and are found in Table I. The oil productive portion of each reservoir is not present in all of the producing wells because their areas and positions vary with respect to one another. Fig. 1 shows the relative position of the four reservoirs and illusIrate? how some wells could penetrate all four, while others are restricted to three. two. or perhaps one. depending on structural location. The first three reservoirs contain undersaturated oil. The deepest. the Elledge, has a primary gas cap. Although this reservoir covers a considerable area of the field. it has a very thin section and a low order of permeability. Elledge producing wells have generally been characterized by an early increase in GOR, making it necessary to recomplete them in other reservoirs. (At present. one well is completed in the Elledge. which is still producing.) Because of the difficulties en-countered in producing oil from this reservoir. and the small quantity of oil actually present. future attempts at producing it will probably be on a salvage basis during the later life of the program. For this reason, the remainder of this report will be confined to a discussion of the Bacon, Hill and pius-burg reservoirs.

Jan 1, 1950

By R. A. Morse, W. W. Owens, D. R. Parrish, T. M. Geffen

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By D. R. Parrish, T. M. Geffen, R. A. Morse, W. W. Owens

Laboratory studies of several factors affecting measurements of relative permeability were made using the three-section plastic-covered core technique. Results show that the core assembly, properly constructed, will perform as a single unit, and that the testing technique will, under suitable conditions of pressure gradient, gas expansion, and migration of partial water saturation, permit measurement of flow characteristics not affected by technique. Wettability equilibrium is readily established in cores exhibiting strong wetting preference to water or oil when initially saturated with water. Laboratory tests must be conducted so that saturation changes represent those that occur in the reservoir. Immediate implications of saturation history are (1:) that the possibility exists of increasing the displacement efficiency of solution gas drive reservoirs over the natural process, and (2) residual gas saturations following water flooding in gas or gas condensate reservoirs will be 15 to 50 per cent pore space rather than 1 to 11 per cent as generally believed. INTRODUCTION Solutions of petroleum reservoir problems pertaining to production performance require the use of true relative permeability characteristics. 'This relationship of fluid conductivity and saturation has been obtained by reservoir engineers in four ways, namely: 1. From past gross reservoir performance and the extrapolation of this data based on experience,1,2 2. By using published fluid flow relationships obtained in laboratory studies on general type porous materials,3, 4, 5 3. By attempting a mathematical derivation of flow behavior," using some experimentally obtained characteristics of reservoir rocks, and 4. By laboratory flow tests using representative rock samples of a reservoir. The first three methods listed above have shortcomings which make their use limited or questionable. Production characteristics of only certain processes are obtained from field data and these are not available at the beginning of a reservoir's producing life, at which time they are desirable. It is fortuitous if general fluid flow characteristics obtained experimentally have accurate application to specific field problems. Also, it is felt that at this time there is not sufficient knowledge of the flow behavior of oil, water, and gas in porous materials to enable applicable analytical description of this to be made based on other measured rock characteristics. Measurement of relative permeability in the laboratory offers the only direct method subject to adequate checking for determination of flow characteristics applicable to field problems. Primarily, this paper deals with laboratory experiments to establish the effects of several factors on the measurement of relative permeability and the practical significance of this knowledge. Laboratory flow tests are essentially model studies; the gross reservoir being represented by a small rock sample. It is necessary to simulate in experiments all the factors of importance which influence flow in the reservoir, as well a.; to eliminate effects peculiar to the model studied to assure measurement of valid flow behavior. Factors which affect the measurement and behavior of fluid flow in porous materials have been studied by other investigators.3,7,8,9,10,11 This analysis is not intended to evaluate fully all factors involved, but to establish first the validity of measurements by the technique used and then study flow behavior under various conditions. The studies reported are as follows: 1. Effects of pressure gradient, 2. Effects of gas expansion in tests conducted at near atmospheric pressure, 3. Effects of migration of a partial water saturation in oil-gas-water systems, 4. Effects If wettability characteristics of the system. and 5. Effects of the fluid saturation history. The first three are important only in laboratory measure-

Jan 1, 1951

By I. Fatt, D. N. Saraf

A method is described for measuring two- and three-phase relative permeabilities in sandstones or sand packs using a nuclear magnetic resonance (NMR) technique to determine fluid saturations. Two- and three-phase relative permeabilities have been determined on Boise sandstone using the NMR technique of saturation measurement. Three-phase relative permeability to water was found to depend only on the water saturation, whereas three-phase permeability to oil depended on both the water and oil saturations. Relative permeability to gas in three-phase flow was found to depend only on the total liquid saturation. INTRODUCTION Three-phase relative permeabilities are extremely useful in calculating field performance for reservoirs being produced by simultaneous water and gas drives. Three-phase relative permeability data are also needed for analyzing solution gas-drive reservoirs which are partially depleted and are being produced by water drive. Some thermal recovery processes involve three-phase flow which require three-phase relative permeability data for predicting reservoir behavior. Unfortunately, three-phase relative permeability measurements have rarely been made. Also, because of the scarcity of three-phase data, it has not been possible to date to relate other measured rock characteristics to the relative permeabilities with a great certainty. Leverett and Lewis,l Reid2 and Snell3 have reported three-phase relative permeability data on unconsolidated sands. Leverett and Lewis used ring electrodes spaced along the length of the sand sample to measure the resistivity of the sample which was assumed to be monotonically related to brine saturation. Gas saturation was determined from pressure-volume measurements. Oil saturation was obtained by material balance on the cell containing the sand sample. This method is involved and time consuming. Another difficulty arises from the fact that the resistivity of the sand is a function not only of saturation of brine but also of the distribution and saturation history of the brine in the pore spaces. Reid2 used a gamma ray absorption technique for measuring liquid saturation. This method has the disadvantage that total liquid saturation rather than oil or brine saturation is all that can be measured and still another method is required to determine the saturations of individual components. snel13 used a neutron bombardment method which also required a separate determination of the individual component saturations. Caudle et al.4 measured three-phase relative permeability on consolidated sandstones using vacuum distillation for determining fluid saturations. Distillation after each reading makes this technique very lengthy and time consuming. Corey et a1. 5 and Naar and Wygal 6 measured three-phase relative permeability on sandstones by the capillary-pressure method. Semipermeable diaphragm assemblies were used at each end of the core specimen to keep the water phase in the core. Gravimetric methods were used to determine fluid saturations. Sarem7 recently reported an unsteady-state method for measuring three-phase relative permeability on sandstones. This method is an extension of Welge's method8 for measuring two-phase relative permeability. Although Sarem's method is simple and comparatively fast, the assumptions involved may oversimplify the problem. Sarem's assumption, that in all rocks relative permeability to each fluid will depend only on the saturation of that fluid, seems to be rather unrealistic. Neglecting capillary effects at the end of the core is also a weak assumption. Donaldson and dean9 measured three-phase relative permeability using a method similar to Sarem's.

By A. M. Gaudin, D. W. Fuerstenau

IN concentration of certain ores by soap flotation, prevention of quartz flotation is desired; the contrary is true in treatment of some oxide iron ores. Experimental study of the flotation of quartz goes back at least a quarter of a century.' Clean quartz does not float with fatty acids or soaps but does float when activated by one of many metallic salts. Control of pH is important. Broadly speaking the problem of quartz flotation has been approached from the empirical side, as was the related topic of flocculation or dispersion of quartz suspensions? Empirical studies indicated the existence of critical relationships between the additions of collector and activator. These additions were not stoichiometric for the formation of soaps of the activator cation. For example, Gaudin and Rizo-Patrona found optimum quartz flotation at pH 10.6 using barium activation and oleate collection when the molar ratio of oleate to barium was 1 to 1 instead of 2 to 1, as would be called for formation of Ba(OL),. Cooke and Digre" ' found that if calcium is the activator, a minimum quantity of that agent is required for effective flotation when the pH is 11.5. In other words, if the concentration of Na' exceeds 10 -2.5 mols per liter or if the concentration of H exceeds 10-11 mols per liter, the concentration of Ca++ in solution required for quartz activation is increased. This suggests that H+ is much more effective than Na+ on 10-2.5 quartz, perhaps in the ratio ofp or 108. Schuh- mann and Prakash6 studied anew the activation of quartz by barium, calcium, aluminum, and ferric iron. Salts of these metals are activators provided they are in stoichiometric excess over the collector used with them. Alkaline-earth salts are effective only in alkaline circuits. Important as they are in giving data on the effect of various agents on quartz, all these studies fail to give information on the detailed structure of the quartz-solution interface. A beginning in this direction was made by Gaudin and Chang,? who measured the adsorption of radioactively marked barium and laurate ions at quartz surfaces, and by Gaudin. Spedden, and Laxen,8 ho measured the adsorption of radioactively marked sodium at quartz surfaces. Work has also been done by Bell0 n measurement of the adsorption of sodium ion and chloride ion at quartz-solution interfaces. In all these experimental measurements of adsorption, the solid was centrifuged or filtered from the bulk of the liquor with which it had been associated; and the composition of the solid surface was ascertained by analysis, after allowance was made for the ionic composition of the liquor included with the centrifuged solids on the assumption that it is identical to the bulk liquid. Adsorption measurements give only the total amount of collector adsorbed at the quartz-solution interface; they give no indication of the distribution of these adsorbed ions at the interfacial layer. It is the ionic structure of the solid-solution interface and its importance to flotation that is the subject of this paper. The structure of this interfacial layer can be investigated by means of electrokinetic methods so that by combining electrokinetic studies with adsorption measurements, a more complete picture of the quartz surface may be obtained. The following studies were made to ascertain how electrolytes used in the soap flotation

Jan 1, 1956

SEC. 1. The membership of the Institute shall comprise seven classes, namely: 1. Members; 2. Honorary Members; 3. Senior Members; 4. Associates; 5. Junior Members; 6. Rocky Mountain Members; 7. Junior Foreign Affiliates. All shall be equally entitled to the privileges of membership, excepting that no member of any class whose residence shall be outside of the United States of America, except those residing in Mexico and Canada, shall be entitled to vote. SEC. 2. Members: A person to be eligible for election or transfer into the class of Member must be at least 27 years of age and must have had at least six years' employ¬ment in the practice of engineering, mining, geology, metallurgy, or chemistry, during at least three years of which he must have held positions of responsibility in one or more of these fields. This shall not apply to Rocky Mountain members. SEC. 3. Honorary Members: Each candidate for Honorary Membership must be recommended by at least ten Members and must be elected by ballot at a meeting of the Board of Directors by the unanimous vote of the Directors present; provided, how¬ever, that the number of Honorary Members shall at no time exceed twenty. Such election shall automatically act as a transfer of such member from any other class of membership to which he may belong. SEC. 4. -Senior Members: The Directors may in their discretion place on the Honor Roll of Senior Members and transfer from any other class of membership other than Honorary Membership the name of any Member or Associate who has reached the age of seventy years and who has paid dues for thirty years, and for good reasons in special cases may vary the age or number of years. SEC. 5. Junior Members: A person to be eligible for election to the class of Junior Member must be qualified through education or experience to hold a subordinate position in engineering, mining, metallurgical, geological or chemical work. He shall be not more than 33 years of age at the time of election. SEC. 6. Associates: A person eligible for election or transfer into the class of Associate shall be one, who, in the opinion of the Committee on Admissions and the Board of Directors, is suitable for such election or transfer by reason of his interest in or connection with mining, geology, metallurgy, or chemistry. SEC. 7. Rocky Mountain Members: Membership in a special class of life member¬ships without annual or other dues and without right to receive the printed literature distributed to other members or the right and privilege of wearing the official badge of technical members, is given to all members of the Rocky Mountain Club at the time of consolidation. These special Rocky Mountain memberships shall be claimable by any member of the Rocky Mountain Club, not already a member of the Institute, availing himself of the privilege within ninety days after mailing of notice to him, by the Secretary of the Institute. SEC. 8. Junior Foreign Afliate: Upon appropriate action by the Board of Direc¬tors and with its approval, members in good standing of any technical society having its headquarters outside of the United States of America, Canada, or Mexico,

Jan 1, 1937

By J. G. Kura, P. D. Frost, L. W. Eastwood

THE preparation and general properties of mag-nesium-lithium base alloys have been described in earlier papers.l,2 Lithium forms solid solutions with pure magnesium, lowers its density, and improves its formability. The improved isotropy and better formability of these alloys are attributed to the ability of lithium to convert the magnesium lattice from hexagonal (alpha phase) to body-centered-cubic (beta phase) structure. This change in structure is, however, accompanied by some limitations which make it difficult, if not impossible, to combine all the desirable properties in one composition. The most important of these limitations is the tendency of the high-strength alloys to overage and lose strength at temperatures of the order of 150" to 200°F. A study was made of the effects of composition and heat treatment on the age-hardening character- istics of the alloys. Stability of properties was determined by hardness and tensile testing of the alloys at room temperature after various periods of exposure to elevated temperatures. Precipitation-hardening curves are shown for a number of magnesium-lithium-zinc alloys in fig. 1. All the alloys were solution treated at 700°F and aged at 200°F. The reason for using the drastic quench, toluene at —105°F, was to reduce the rapid precipitation of the hardening phase which takes place at room temperature. Previous experience has shown that a hardness of about 90 to 95 Rockwell E is indicative of yield strengths in the range of 35,000 to 40,000 psi. This is a desirable strength level for magnesium-lithium base alloys with specific gravities of the order of 1.65 or less. Although the hardness level is raised by large zinc contents, a corresponding decrease in the cold formability of these alloys occurs with increasing zinc content. Thus, alloys containing up to about 10 pct Zn and having hardnesses of the order of 70 to 75 Rockwell E may be bent over a very small radius; however, the 16 pct Zn alloy requires a bend radius of more than 8T. The hardness relationships illustrated in fig. 1 can be explained by the partial phase diagram shown in fig. 2. The zinc-free magnesium-lithium alloys are entirely body-centered cubic (100 pct beta phase) when the lithium content of the binary is 10.3 pct or higher. When zinc is added, the boundary between the beta and alpha-plus-beta fields at 700°F is shifted to lower lithium contents. In addition, the solubility of zinc at 700°F decreases with decreasing lithium content. It is shown by a study of micro-structures that the limit of solid solubility of zinc in the 6Mg/Li* matrix at 700°F is about 19 pct. It is believed from a study of the aging curves that this limit is about 2 to 3 pct at 200°F. Zinc additions up to about 2 pct increase the hardness and strength of the magnesium-lithium base solid solution. Larger additions of zinc effect further hardness increases, but precipitate during prolonged aging at 200°F. Alloys having 14 to 20 pct Zn precipitation harden extremely rapidly during quenching, even when quenched in toluene at —105° F. The high-zinc alloys overage at 200°F but are capable of maintaining reasonably high hardnesses for periods up to 1000 hr.

Jan 1, 1951

By John B. Myers

Vermiculite is the commercial name used to describe a micaceous mineral that expands appreciably when heated. This process, called exfoliation, results in a light weight material. The light weight material is also called vermiculite, or more exactly, expanded vermiculite. Practically all uses of vermiculite are for the expanded material. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit and a perfect basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. The hardness varies from 1.5 to 2 or more, depending on the composition. The specific gravity varies from 2.2 to 2.7; specific heat 0.2; fusion temperature 2,000° to 2,500°F; luster pearly to greasy; color amber, bronze, brown, dark green, and black. Feel is like talc and sometimes soapy when wet. When heated quickly at elevated temperatures, vermiculite exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin vermiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted to steam. The increase in bulk volume of commercially prepared material is 8 to 12 times, but individual flakes may expand as much as 30 times. There is no expansion parallel to the cleavage. Vermiculite may also be expanded by several chemical processes such as soaking in hydrogen peroxide, weak acids and other electrolytes. The color changes during expansion. Heat-treated material changes to a light golden bronze or cream color depending on composition. The conditions of heating affect color. Heating in an oxidizing atmosphere produces reddish colors and heating in a reducing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. Vermiculite is hydrated magnesium-aluminum silicate. Although there has been much research on the chemical and structural composition, there is not yet complete agreement on the exact formula and composition. This is to be expected since vermiculite is not a mineral of fixed composition and different workers have examined different varieties. It has been proposed that vermiculite is not a single species but a family of related minerals. This has also resulted in many names for the particular vermiculite found in a certain deposit. All of this difficulty arises from the very nature of its crystal chemistry. Unlike most minerals, certain crystal structure properties and the chemical composition can be changed by the ordinary forces of nature or in the laboratory. This would suggest that vermiculite be thought of more as a variable mineral rather than a group of related species. It was stated on page 261 of this volume in the chapter on Clay Minerals by H. H. Murray of the Georgia Clay Co., that vermiculite is an equidimensional, expandable clay mineral. Gruner (ref. 14, Chap. 12) showed that the structure consists of a layer made up of two silica tetrahedral sheets with a central magnesium, iron octahedral sheet separated by two layers of water molecules and adsorbed magnesium and calcium ions. Mathieson and Walker,2a in a recent publication, agree that vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation ex-

Jan 1, 1960

By Robert Y. Grant

This study outlines the history of metal mining in Japan and the characteristics of the industry as they existed from 1925 to 1945. Mining and milling operations are described together with the role of the Japanese Government. A description of post-hostilities conditions and the present state of the industry is included. MANY of Japan's larger and better known mines date back to the early centuries of the Christian Era. The first stimulus to mining in Japan came through the growth of Buddhism, A. D. 600 to 700, and the attendant need for copper and other metals for temple ornaments and statues. During the Feudal period, 1333 to 1568, mine operations were expanded to meet the demand for ornament metal and for financing of campaigns. After removal of the seat of government from Kyoto to Tokyo, about 1600, the Tokugawa Shogunate placed great emphasis on mining, and many new mines were opened, some of which are still operating. Toward the end of the Tokugawa period, mining had declined sharply from its earlier peak. The easily worked, high grade portions of the orebodies had been exhausted, and the mining techniques then available could not exploit the deeper, lower grade ores. Similarly, extraction of metal from the sulphide ores presented a major problem. With the Meiji Restoration in 1868 and the rapid opening of the country to western ideas came a rejuvenation of the mining industry. Mining, milling, and smelting processes were greatly improved, resulting in the extension of development work into hitherto inaccessible portions of orebodies. The demand for metal during World War I stimulated activity throughout the industry; copper mining, particularly, expanded to a point where Japan ranked second among world producers.* During the depression following the war, mining underwent a severe contraction in activity, recovering slowly during the late 1920's only to undergo a further setback in the worldwide depression which started in 1929. Mineral output declined in 1930, but the beginning of Japanese expansion, 1931 to 1932, brought about an increase in the output of mine products starting between 1932 to 1934. Production continued to rise, the peak output being attained 1939 to 1943 in virtually all commodities. The greatest production of iron ore, chromite, and manganese was not experienced until 1944 when blocked imports, coupled with strong demands for steel, provided the needed incentive. Through necessity, Japan produced much of her mineral needs from her own mines at high cost during World War 11. Taking the 1932 to 1936 period as an average, however, Japanese mines produced only 16 pct of the iron available to industry, 8 pct of the lead, 33 pct of the zinc, and 68 pct of the copper. Nearly all of Japan's output of gold, silver, copper, lead, and zinc between 1925 and 1945 came from 30 to 49 pct of the mines for which production data are available; for example, 66 of 174 gold-silver mines accounted for 98 pct of the output of this group. Further analysis of mine output indicates that a large part of Japan's metal output was derived from a few large mines; about 10 gold-silver, 15 copper, 3 lead-zinc, 5 manganese, and 2 iron mines account for most of the production. Many of these mines have been operated for 200 to 400 years. With the

Jan 1, 1952

By Fred D. Gustafson

With the postwar emergency for new housing and for new industrial buildings, much research has been done on lightweight aggregates for use in concrete and plaster. The trend toward lighter weight aggregates to relieve the dead load on the higher, steel framework buildings started toward the end of the last century. Progressively the requirements became more stringent, crushed bank slag, weighing 80 lb per cu ft as compared to 100 lb for crushed rock, was supplemented in some sections by foamed slags and expanded shales weighing from 40 to 60 lb per cu ft. In other sections cinders were used weighing from 40 to 50 lb, including sand. Sections favored with more recent vulcanism turned to pumice weighing from 30 to 60 lb, whereas other localities made use of diatomite, from 28 to 40 lb. Exfoliated vermiculite weighing from only 6 to 10 lb per cu ft came into use. As the search for lighter weights in aggregates continued so did the search for other desirable properties such as nailability, ease of cutting or channeling, and good insulation to both sound and heat. This search eventually led to a widespread interest in the expansion of perlite, or similar volcanic glasses, with the result that in 1946, the Office of the Housing Expediter' listed eleven firms reporting the operation of processing plants either on pilot or commercial scale producing aggregates weighing from 2 to 16 lb per cu ft. Geology Perlite is one of the large family of rocks originating from a granitic or acidic magma and generally has a "rhyolitic composition with a marked perlitic structure."² The name "perlite" is a derivation from "perlstein" originally given "to certain glassy rocks (hyaloliparites, hyalo-rhyolites) with numerous concentric cracks, from the fancied resemblance of broken out fragments to pearls."3 The cause of the perlitic texture is somewhat controversial. Johannsen attributes the texture to strain set up in the glass by cooling and describes the finding of peculiar, glassy balls, called marekanite, more or less rounded and showing concave indentations, which may be left when perlite is broken. Frank Rutley, on the other hand, in 1881, while working on vitreous rocks from Montana, observed that there was incipient or partially started crystallization with segregation of water toward the un-crystallized portion in all specimens of perlite examined. Further he observed evidence of strain around focii of crystallization to which he ascribed the development of the spherical cracking which gives the rock its perlitic texture.4 Widespread over the western and southwestern United States where Tertiary vulcanism is exposed, perlite commonly is associated with andesitic, basaltic, and rhyolitic lavas with inter-bedded tuffs and ash of Eocene age although some deposits are associated with rocks assigned to the Pliocene age.5, 6 n nearly all cases the perlite overlies water laid tuff beds or agglomerates or breccias of explosive nature, an outstanding exception being the occurrence of perlite as the chilled selvage of andesite intrusions.7'8 Available chemical analyses of per-lites from the western and southwestern United States indicate that they are varieties of leucorhyolites rather than of normal rhyolites, leucorhyolites having less than 5 pct of dark minerals, normal rhyolites having more than 5 pct. This conforms with Johannsen's observation that leucorhyolites are the prevailing kind in North America.9 Tables 1 and 2 give

Jan 1, 1950

By W. L. Falke, A. A. Cochran

A basic problem in connection with manganese is to find economical ways to utilize domestic resources. As a part of its program to conserve domestic mineral resources and to reduce dependence of foreign sources, the Bureau of Mines had conducted extensive research to broaden manganese technology and to find economical, technically-feasible processes for recovering manganese from these low-grade resources. This paper analyzes some of the major difficulties which have been encountered in previously proposed processes for treating low-grade manganese ores and discusses a process which may circumvent many of these difficulties. Vast deposits of low-grade manganese ore exist in the U.S., yet domestic production is insignificant compared to the more than 2 million tons of ore imported yearly into this country.' A basic problem in connection with manganese is to find economical ways to utilize domestic resources.2 As a part of its program to conserve domestic mineral resources and to reduce dependence on foreign sources, the Bureau of Mines has conducted extensive research to broaden manganese technology and to find economical, technically feasible processes for recovering manganese from these low-grade resources. Although a great many processes have been proposed for treating domestic manganese resources, a failing of many of them is that too many steps are involved for economical operation.' Some of the major processes that have been proposed were reviewed by Norman and Kirby.3,4 Chlorination processes have become increasingly useful as a means of recovering valuable metals from raw materials, because the relative cost of chlorine (Cl2) and hydrogen chloride (HC1) has decreased through the years, and because the corrosion resistance of materials of construction has been improved. The objective of these processes is to form metal chlorides that are more volatile or water-soluble than are the corresponding oxides or sulfides; these compounds then can be separated from the gangue or other minerals by volatilization or leaching. Several chlorination processes for the recovery of manganese have been investigated by the Bureau of Mines5-8 and others; the major chlorination processes were reviewed in 1963, and their main features were compared.4 In all these processes, the simultaneous leaching or volatilization of iron chlorides with manganese chloride (MnCl2) is a problem, and the more iron that is present, generally the greater the problem. The leaching step is not highly selective, and the product of this step is, at best, suitable only for the production of ferromanganese or for further processing to remove iron. The product of the volatilization step is, in all cases, a mixture of iron and manganese chlorides that contains too much iron even for ferromanganese production, and must undergo additional processing steps for iron removal. THERMODYNAMIC CONSIDERATIONS The literature indicates that the desired chlorination reactions will proceed at practical rates at temperatures near 1200°K (927°C). Free energy changes at 1200°K for the critical steps of the reduction and chlorination reactions9-11 follow: Most of the research on chlorination processes for manganese recovery has been done with HC1 rather than with C12, for the following three main reasons: 1) Recycling of the chlorinating agent, which is economically vital, appeared to be easier for HC1

Jan 1, 1968