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By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By H. F. Ramstad, F. D. Richardson

The equilibria (a) SiOz +Hz =SiO +H20 and (b) Si + SiO, = 2Si0 have beet1 studied at temperatures of 1425"to 1600°C ad 1310°to 1485°C respectively. The stattdard free energy changes for the tzrro reactions are given by the equatiotts Combination of the results for both equilibria leads to tiotz removes certain anomalies in existing high-terlzperature data for equilibria involving silica and silicon in iron. In many metallurgical processes and in many laboratory investigations silicon monoxide undoubtedly plays an important role. It is unfortunate therefore that wide differences exist between the results obtained by different investigators1-7 in their studies of such equilibria as In an attempt to put our knowledge of SiO on a surer basis, an exhaustive study has been made of equilibria [I] and [2] at temperatures ranging from 1300" to 1600°C. Reaction [I] was studied by measuring the amounts of silica which could be condensed from streams of Hz or Hz + HzO which had previously been brought into equilibrium with silica at temperatures ranging from 1425" to 1600°C. Reaction [2] was studied by measuring the material that could be condensed from streams of Hz or argon which had been brought into equilibrium with mixtures of silicon and silica at temperatures ranging from 1310" to 1485°C. EXPERIMENTAL Materials. The silicon was "superpure" grade and contained less than 0.1 pct impurities. The silica was prepared from pure mineral quartz; this was crushed and treated with concentrated hydrochloric acid to remove particles of iron, washed with water, and finally dried at 120°C. For the hydrogen + silica reaction, the silica was sized to —20+100 mesh. For the silicon + silica reaction, the two materials were ground to a fine powder in an agate mortar. The hydrogen and argon were commercial oxygen-free gases. The gas streams were controlled with capillary flow meters and the volumes were measured by wet gas meters. After passing through the meters, the gases were partially dried by silica gel. The hydrogen for the HZ + SiOz reaction was then passed through palladised asbestos at 300°C and dried with magnesium perchlorate. The efficiency of oxygen removal was checked throughout the experiments by passing the gas over an electrically heated strip of nichrome, used as an indicator as described by Rathman and de itt.' When mixtures of HZ + Hz0 were required, the partial pressures of water vapor (1.8 to 22 mm) were obtained by passing the hydrogen through oxalic acid dihydrateg' lo held at various controlled temperatures, O.l°C, by means of a water bath. The hydrogen for the Si + Si02 reaction was purified by passing it over a mixture of 3 parts of magnesium to 5 of lime heated to 600°."l1 u The argon for this reaction was passed through titanium powder (-3/16 in. + 100 mesh) heated to 900°C. The nitrogen used to prevent the reaction products escaping from the condenser (see later), was deoxidized by copper or iron at 600°C. All these gases were finally dried with magnesium perchlorate. Furnace, Temperature Contr01, and Measurement A molybdenum resistance furnace was used for both sets of experiments. The reactions were conducted inside a high-grade alumina tube, 36 in. long and 1 in. in diam as indicated in Fig. 1. With this arrangement an even temperature zone (2"C) 4 cm long was satisfactorily obtained. The temperatures were kept constant by means of a proportional controller actuated by a Pt-Pt 13 pct Rh thermocouple. This was placed between the two alumina tubes, so that the temperature at the junction was 1400" to 1450°C. Up to 1485"C, the temperatures were measured with Pt-Pt 13 pct Rh thermocouples. For higher temperatures an optical pyrometer was used, this being sighted (through the glass window 1 in Fig. 1) on the end of the alumina tube, that held the SiOz or Si +SiOz mixture, 10 in Fig. 1. The optical pyrometer was recalibrated whenever a change was made in any part of the apparatus situated in the hot zone. Successive readings with the optical pyrometer were reproducible to within 1"C. Equilibrium Apparatus and Procedure. Hydvogen and Silica Reaction. The apparatus is shown in Fig.

Jan 1, 1962

By R. Grierson, L. J. Bonis

The high-temperature Strength oF TD nickel has been observed to be dependent upon the previons thermal and mechanical history of the material. Variations in both the level and the anisotropy of strength have been observed. 01 this paper- these variations are correlated with the storing of annealing resistant elastic strain energy in the matrix of the TD nickel. An x-vay line -broadening tecknique is used to measure the maLrTis elastie strain. THE inclusion of a finely dispersed second phase into a ductile matrix has long been recognized as an extremely effective method of strengthening the matrix both at high and at low homologous temperatures. It has been found, however, that the factors which determine the high-temperature strength are not the same as those which are important at low temperatures. Below 0.5 Tm the size and distribution of the second phase particles are of prime importance in determining the strength,')' while above this temperature the strength is mainly dependent upon the previous thermal and mechanical history of the alloy,3-7 This paper is primarily concerned with explaining the response of the high-temperature mechanical strength of one of these alloys (DuPont's TD nickel) to various thermo-mechanical treatments. It will be shown that this response is not associated with the occurrence of any form of dislocation substructure within the matrix of the alloy. It has been found, however, that a correlation does exist between the elastic strain level in the matrix and the previous thermomechanical history of the alloy and that the observed changes in elastic strain level parallel the measured changes in high-temperature strength. It therefore must be concluded that variations in high-temperature strength are a direct result of the variations in elastic strain level. MATERIAL TD nickel contains approximately 2 vol pct of Tho2 in an unalloyed nickel matrix. It is formed, as a powder, by a chemical technique and this powder is compacted to form ingots which are then extruded to give 21/2-in.-diam rod. Rod of smaller diameter is prepared from the as-extruded rod by swaging. In the studies reported in this paper, 1/2-in.-diam rod was used. This rod received an anneal of 1 hr at 1100°C prior to being used in any of these studies. EXPERIMENTAL TECHNIQUES Two methods were used to examine the structure of the nickel matrix of the TD nickel. These were: 1) transmission electron microscopy; 2) the analysis of the position and profile of X-ray diffraction lines obtained using the nickel matrix as the diffracting media. To prepare thin foils for electron-microscopical examination, slices of TD nickel approximately 0.050 in. thick were cut from the as-received 1/2-in.-diam rod. These were then chemically polished down to 0.045 in., rolled to 0.009 in., given a predetermined heat treatment, and thinned, using a modified Bollman technique, to provide the foils for observation. All observations were carried out at 100 kv, using a Hitachi HU-11 electron microscope. Specimens of the undeformed rod were prepared by grinding down the 0.050-in.-thick slices to approximately 0.015 in. and then thinning chemically and electrolytically to give the thin foils. The X-ray specimens were prepared by rolling 0.375-in.-thick rectangular blocks down to 0.075 in. The surfaces of the rolled material were ground flat, chemically polished to remove the layer disturbed by the grinding, and given a predetermined anneal in an inert atmosphere. They were then ground lightly to check their flatness and given a final chemical polish prior to being examined. The X-ray diffraction line profiles were measured using an automated Picker biplane diffractometer. A special specimen holder was built to allow a more accurate and reproducible positioning of the specimen. The line profiles were determined by carrying out intensity measurements at intervals of either 1/30 deg or 1/60 deg over a range of 3 deg on either side of the nickel peaks of interest. A piece of pure nickel which had been recrystallized to give a large grain size was used as a standard to give the X-ray line profile generated by a strain-free matrix. The analysis of the X-ray diffraction line profiles is a modification of that due initially to Warren and Aver-bach8and has been described elsewhere.3 This analysis gives a measurement of two parameters associated with the structure of the nickel matrix. These parameters are: 1) the size of the coherently diffracting domains within the nickel matrix; 2) the magnitude of the elastic strains in these domains. Both of these parameters are first determined in terms of a Fourier series. These series are obtained from other Fourier series which describe the measured profile of the X-ray diffraction lines. Thus, for both the coherently diffracting domain size and the elastic strain level, it is possible to plot Ft (the Fourier coefficient) against t (the term in the Fourier series), where t can be expressed in terms of a distance L and the Fourier coefficient Ft(S) (associated with elastic strain level) can be expressed in terms of the root mean square strain (e2)1/2. Thus a plot of (F 2)1/2 vs L can be obtained. Plots of this type are shown graphically in Figs. 6 and 8. Interpretation

Jan 1, 1968

By Rollin A. Slater

This paper presents a composite of ideas on materials handling systems by describing the design of an over-all system for a hypothetical steel pellet plant located on the Great Lakes. The bulk materials handling industry has served for years as the skeleton and the central system of nerves and nourishment for the body of basic industries. During the past two decades, this body has undergone substantial growth and mutation to meet the surging demands of our national economy for more and better products. The steel industry has kept pace with spiralling demand by innovation which has resulted in new processes and improved designs which generally yield greater production from fewer units. Materials handling technology has likewise improved its techniques and currently has a new, stronger generation of equipment to perform its necessary supporting function. Drawing upon excerpts from several recent plant designs, this paper describes a basic approach to the selection and application of modern bulk materials handling systems to an entirely new steel plant. Specific details are not available for publication, and therefore the plant described herein is a composite of ideas. This imaginary plant will be located on the United States side of the Great Lakes and its owner will be called the Hypothetical Steel Corp. for purposes of discussion. TYPES OF EQUIPMENT The basic bulk materials handling systems and components required in a plant so situated are: lake boat unloaders; railroad train unloading systems; storage pile stackers and reclaimers; large bins and regulating feeders; and the conveyor systems — with their attendant controls— which connect the foregoing. PROGRAM OF DEVELOPMENT The initial work on the plant must be that of the process engineers who develop and refine the basic data, i.e., the logistics of all raw materials, waste materials and products within the plant. During this phase of study, the materials handling engineer may advance his planning only in basic areas such as movements at the dock and movements at the railroad. This initial planning work is concerned only with defining logical plant locations in the light of channels, currents, existing traffic, governmental regulations, locations of existing railroads and available rights-of-way. These systems alone have their own individual criteria which must be respected and accommodated in the final layout. All other elements, such as the arrangement of the blast furnaces, power house, coke plant, by-product plant, scrap preparation plant, BOF shop, and facilities for continuous casting, degassing, calcining, etc., are dictated by their own specific needs and their relation to each other. In the arrangement of these latter facilities, the materials handling system is secondary and must be designed to accommodate. BASIC LOGISTICS The result of the process engineer's work can be expressed in terms similar to those shown in Table I. Plants are customarily rated in terms of annual tons of ingots. Therefore, the basic size of this plant can be determined by referring to the BOF Shop wherein it is sized at 5 million tpy. From the base, the required hot metal can be traced to the blast furnace, which in turn indicates the amount of required flux, iron bearing materials and coke —which in turn establishes the demand for coal. Likewise, the total demand for flux can be determined by the combined demand of the lime plant and blast furnace. The generation of fines and waste products, which have significant value but are not usable as such, create the need for a sintering plant. From projections such as the foregoing, the complete flow of materials can be established and accommodated. The basic premise upon which this typical materials balance is predicted is that the plant will be a producer of high tonnages of non-SpecialtV- products. All basic raw materials (flux bearing, iron bearing, coal) will be prime quality. For example, the basic iron charge will be pellets, and the iron ore fraction will be sized lump, all of which

Jan 1, 1970

By T. F. Bower, M. C. Flemings, H. D. Brody

A series of experiments are reported which show thai reasonable assumptions for analysis of solute redistribution in solidification of castings and ingols illclr(de: negligible undercooling before nuclcation of solid phases, negligible increase of solute in advance of the tips of growing dendrites, complete diffusion within the Liquid oer distances the order, of dentrite arm spacings, platelike dentrite t/o?$holog?.. Qzmli/ali,e and periment is obtained JOY Al-Cu alloys front measurements of amount of nonequilibrium second phase, minimum solute content at the centers dentrites arms (after solidification), and 3) change in minimum solute content in dentrite arms during solidification. In a previous paper' analyses were given describing solute redistribution in dendritic solidification. The analyses were undertaken primarily to permit prediction of "severity of microsegregation" in a casting or ingot after solidification and cooling to room temperature, but can also be used to predict "local fraction solid' as a function of temperature in the solidifying alloy. Numerical results were given for Al-Cu alloys. The aims of this paper are to examine the validity of some of the assumptions of that analysis, and to compare predictions of the theory with experiments. All experiments reported are on Al-Cu alloys, the bulk on Al-4.5 pct Cu alloy. EXPERIMENTS Experiments conducted were on small ingots, 41/2 in. in diam by about 10 in. high. solidified in a controlled thermal environment (i.e., in a resistance-heated, re-circulating air furnace, whose temperature could be controlled to 1°C). In one series of experiments, the ingots were solidified very slowly (solidification time was varied from 8 to 1000 hr) and at constant rate of heat extraction. In a second series of experiments the ingots were solidified ( 'unidirectionally". Fig. 1 is a sketch of the method of making the two different types of ingots. The unidirectionally solidified ingots were fully columnar, and the slowly solidified ingots had equiaxed structures, Fig. 2. In making the slowly solidified ingots, the mold employed was carbon steel, coated with inert refractory. Typically the mold and its environment were heated to 700°C. The molten alloy was then poured into the mold and the temperature of the system equilibrated above the liquidus. The environment of the mold was next cooled with a controller responding to a differential thermocouple that measured the difference between the temperature of the melt and the temperature of the mold environment. The differential thermocouple consisted of one chromel-alumel junction in the melt connected in opposition with a second junction in the furnace. The potential across the differential thermocouple was input to the controller which acted to keep this potential at a set. constant value; hence the temperature difference between the two junctions was maintained nearly constant. Major resistance to heat flow in the above apparatus was between the metal surface and the furnace atmosphere, not in the metal itself. By maintaining a constant temperature difference between the metal and the furnace atmosphere, the controller maintained an essentially constant rate of heat extraction during solidification, regardless of amount of heat released by the metal per unit temperature change. When the metal temperature dropped just below the eutectic temperature. the ingot was removed from the furnace and water-quenched. The unidirectionally solidified ingots were cast in a similar mold to the foregoing except that provision was made to extract heat through the bottom face of the mold by passing air or water through the mold base, Fig. 1. For these experiments, metal and mold temperature were again equilibrated above the liquidus. Temperature of the mold environment was then held

Jan 1, 1967

By S. Nakajima, H. Okazaki

Quantitatiue studies of the deformation texture in drawn tungsten wives were made by the X-vay dif-fractottletetr. Experimental results show that the diffraction Intensities are equal to tilose pvedicted from the (1 10). fiber lexlure but the angxla), spreads of. diffraction peaks in the pole distribution curres are different for different diffraction planes and directions. For this reason a modified (110) fiber lextuve model, in which a kind of anisotropy is assumed, is proposed to explain the results. According to this model the poles lying on a line directing front the (110) to the (110) poles in the (1 10) standard stereograpllic projection should show spreads which are different from those lyitlg on a line directing from the (001) to the (001) poles, which is confirmed by the experiments. The anisolvopy and the spveads of the pole positions are large at the outer part of the wires and decrease gradually lowards the inside of the wire. The possibilily of occurrence of such anisolropy in irrelals with fcc stvuctures is discltssed. THE deformation texture of drawn tungsten wires has been assumed by different investigators to be the simple ( 110) fiber texture.' Recently, however, Leber2,3 has shown that a swaged tungsten rod has a cylindrical texture. It changes gradually to the (110) fiber texture by drawing through dies. However, even after drawing to 0.25 mm in diam, the cylindrical texture can still be found in wires together with the (110) fiber texture. This was deduced from the pole figures obtained from the longitudinal section of these wires. Use was made also of quantitative measurements of the pole distribution curves. Leber stated that the angular spread of the pole distribution curves (henceforward called dispersions) are quite different for (400) 45 deg and (400) 90 deg: the former is always larger than the latter. This inequality is accompanied by deviations of the diffraction intensities from the theoretical values for the ( 110) fiber texture. Bhandary and cullity4 have reported similar results on iron wire and explained them by assuming a cylindrical texture. Both Leber3 and Bhandary4 used only the results of the (400) reflection for the determination of the dispersion. The pole figures found by Leber3 and by Rieck5 are largely different. The model given by Leber to explain the effects is in the authors' opinion in some respects unsatisfactory, especially if one looks at other than the (400) reflections. Intensities and dispersions of diffraction peaks are conclusive factors for the determination of the fine structure in wire textures. For this reason we studied them extensively to come to a model which is more suitable to fit the facts. In the following, after giving the experimental set-up, we report about measurements of X-ray diffraction on drawn tungsten wires. Different models to describe the experimental results will be discussed. EXPERIMENTAL GO-SiO2-A12O3 doped tungsten wires drawn to 0.18 mm in diam were used for the measurements. The wires were chemically etched to various diameters down to 0.03 mm. Measurements were carried out for the different wires in order to determine the dependence of the texture on the radius. The wires were cut to pieces of 10 mm length and fixed with paste closely against each other on a flat, polished glass plate. Parallelism of the wires with the surface of the glass plate should be adequate. For the diffraction studies three different X-ray sources were applied, respectively, giving the CuK,, FeK,, and FeKp emission. The measurements were carried out with a diffrac-tometer with a GM counter. The latter was fixed to a certain diffraction angle 20hkl and the diffraction intensity was recorded as a function of the angle of rotation of the specimen around the axis, lying in the specimen surface and perpendicular to the wire axis, as shown in Fig. 1. Measurements were also done with the detector at angles slightly deviating from the diffraction maxima The measured intensities in this case were taken to be equal to the background level. The deviations were chosen as small as possible but large enough to eliminate the influence of the diffraction maxima. The useful range of the rotation angle x of the specimen is generally limited by the wavelength of the X-rays. We have: where and cp is the angle between the wire axis and the normal of the diffraction plane. Intensity measurements were made to find the necessary corrections for counting loss of the GM counter and for distortion resulting from such effects as absorption of X-rays and from inclination of the reflection plane under study with respect to the surface of the specimen. The counting loss was esti-

Jan 1, 1968

By D. S. Flett, D. W. West

The solvent extraction of chromium 111 has been studied for the system Cr 111, H,SO., H,O/RNH/RNH., xylene, where the primary amine used was Primene JMT. Rate studies have shown that extremely long equilibrium times are required, ranging from 1 hr at 80°C to 20 days at room temperature. Heating the solution prior to extraction increases the rate of extraction. The variation in the amount of Cr 111 extracted is an inverse function of the acidity of the aqueous phase. Thus, the slow rates of extraction appear to be connected with the hydrolysis of the Cr I11 species. Extraction isotherms for the extraction of Cr 111 have been obtained for two sets of experimental conditions, namely at 60°C and for a heat-treated solution cooled to room temperature. The separation of Fe 111 from Cr 111 and Cr 111 from Cu 11 in sulfate solution by extraction with Primene JMT has been studied and shown to be feasible. A survey of the literature relating to the solvent extraction of chromium showed that, although many systems exist for extraction of Cr VI, only a very few reagents have been found to extract Cr 111. The extraction of Cr III by di-(2-ethyl hexyl) phosphoric acid has been reported by Kimura.' A straight-line dependence of slope —2 was observed between log D,, and the log mineral acid concentration at constant extractant concentration. Since the slope of this plot reflects the charge on the ion extracted, it must be concluded that a hydrolyzed species of Cr III is being extracted. Carboxylic acids generally do not form extractable complexes with Cr III but di-isopropyl salicylic acie does extract Cr 111. Simple acid backwashing of the organic phase, however, failed to remove the chromium. Similar difficulty in backwashing was found by Hellwege and Schweitzer8 in the extraction of Cr I11 with acetyl-acetone in chloroform. The extraction of Cr 111 from chloride solutions by alkyl amines has been reported4-' but the maximum amount of extraction achieved in these studies did not exceed 10%: From sulfate solutions, however, Ishimori" has shown that appreciable amounts of Cr I11 were extracted by amines. The amines used were tri-iso-octyl amine, Amberlite LA-1 (a secondary amine, Rohm & Haas) and Primene JMT (primary amine, Rohm & Haas). The efficiency of extraction with regard to amine type was primary>secondary> tertiary. Appreciable extraction of Cr I11 was recorded for Primene JMT as the aqueous phase acidity tended to zero. The major difficulty with Cr I11 in solvent extraction systems stems from the nonlabile nature of the ion in complex formation. This accounts for the slow rate of extraction generally experienced and the difficulty encountered in backwashing the Cr I11 from the organic phase in the case of liquid cation exchangers. Consequently, the possibility of extraction of Cr I11 as a complex anion is attractive since the backwashing problems should be minimized in this way. From published data, it appeared that the extraction of chromium from sulfate solutions of low acidity by primary amines afforded the best chance of success for a useful solvent extraction system for Cr iii This paper presents the results of a study of the extraction of Cr I11 from sulfate solution by Primene JMT and examines the application of such an extraction procedure for the recovery of chromium from liquors containing iron and copper. Experimental Chromium solutions were prepared from chrome alum in sulfuric acid and sodium sulfate so as to maintain a constant concentration of sulfate ion of 1.5 molar. Solutions of Primene JMT were prepared in xylene and the amine equilibrated with sulfuric acid/sodium sul-fate solutions, of the same acidity as the chromium solution, until there was no change in acidity between the initial and final aqueous phases. The solutions of Primene JMT conditioned in this way were then used for the equilibration experiments. Equilibrations at 25°C were carried out in stoppered conical flasks shaken in a thermostat; equilibrations at all other temperatures were carried out in stirred flasks in a thermostat. After equilibration, the phases were separated and analyzed for chromium. In the tests on the rate of extraction, small samples of equal volume of both phases were withdrawn from time to time and the chromium distribution determined. The chromium analyses were carried out either coloi-imetrically using diphenyl carbazide, or volu-metrically using addition of excess standard ferrous ammonium sulfate and back titration of the excess iron with potassium dichromate. The oxidation of Cr 111 to Cr VI in the case of the raffinate solution was effected by boiling with potassium persulfate in the presence of silver nitrate and, for the backwash solution, by boiling with sodium hydroxide and hydrogen peroxide. Results Preliminary experiments indicated that extraction results were effected by the age of the chromium solution, higher distribution coefficients being obtained with solutions which had been allowed to stand for some time. Consequently a stock solution of chrome alum, 10 m moles per 1 Cr I11 in 1.4 M Na,SO,/O.l M &SO,,

Jan 1, 1971

By J. E. Dorn, L. A. Shepard

LOW and Gensamer' demonstrated a number of years ago that the yield point phenomenon in mild steels was associated with the presence of fer-rite soluble carbon or nitrogen. More recently the yield phenomenon in body-centered-cubic metals containing interstitials was rationalized by Cottrell' in terms of a simple dislocation model. Interstitial atoms interact with dislocations in two ways; they cause not only local expansions but induce local tetragonality in the lattice. Consequently, interstitial~ interact with the hydrostatic tension and shear components of the stress about dislocations. They tend to migrate toward the expanded regions of edge dislocations and to assume sites that relieve the shear stresses of screw dislocations. Thus, a dislocation saturated with solute atoms constitutes a lower free energy state than that obtained when the dislocation threads through the average composition regions of the matrix. A greater stress will be required to separate the dislocation from its atmosphere than to move the dislocation through the matrix. This factor gives rise to the upper yield stress, which is required to unleash a series of dislocations in a localized region. This local yielding is propagated across the specimen to form a thin band of plastically deformed material known as a Lueder's band, making an angle of about 45" to the stress axis. Once the band has formed, deformation continues at the lower yield stress by the spreading of the Lueder's band in the direction of the applied stress. Undoubtedly the spreading of Lueder's bands at the lower yield stress is accomplished by the high stress concentrations at the band fronts, which serve to induce continued unlocking of new dislocations in advance of the migrating band fronts. Cottrell and Bilby have shown that the dependence of the yield point on temperature can be deduced by assuming that thermal fluctuations aid the stress in unlocking small dislocation loops from their solute atmospheres. Once a loop that exceeds a critical size has been nucleated, the entire locked diqlocation is released and can migrate. Fisher4 simplified this analysis by assuming that the locking forces were short range, so that if the dislocation loop were displaced only one Burgers vector from its atmosphere, it would be unlocked. Applying his model to the special case of delayed yielding under a constant stress of the order of the upper yield strength, he demonstrated that the delay time 7 for yielding should depend on stress and temperature according to where A and B are constants, G is the shear modulus, and u and T are the resolved shear stress and absolute temperature, respectively. Cottrell and Bilby, Fisher, and Fisher and Rogers' have shown that the above deductions are at least in qualitative harmony with the experimental facts. A number of investigators5-0 have shown that the yield point phenomenon can also be induced in sub-stitutional alloys of face-centered-cubic metals. In general such yield points are not as pronounced as those encountered in body-centered-cubic metals containing interstitials. The yield point phenomenon in these materials is usually enhanced by prestrain-ing at low temperatures and aging at intermediate temperatures. Undoubtedly the yield point phenomenon induced by strain aging substitutional alloys also results from locking of dislocations. But the locking of dislocations in substitutional alloys of face-centered-cubic metals differs somewhat from interstitial locking of dislocations in body-centered-cubic metals. Substitutional elements in face-centered-cubic lattices cause only radial displacements of the adjacent lattice points. Consequently, only the edge components of dislocations can be locked by the mechanism suggested by Cottrell. Additional locking, however, can be obtained by the Suzuki mcchanism.10 In face-centered-cubic metals, dislocations exhibit lower energies when they are present in the

Jan 1, 1957

By Milton E. Wadsworth, W. Martin Fassell, William H. Dresher

A study of the rate of dissolution of molybdenite (MoS2) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process. HIGH temperature-high pressure techniques have long been used to great advantage in the organic chemical industry, the petroleum industry, and the paper industry. Only recently, however, have these methods been used to extract metals from their ores on a commercial scale. The Chemical Construction Corp., together with interested producers of nickel and cobalt, has done much to develop methods of producing nickel and cobalt powders by the use of high temperature-high pressure techniques.' The Howe Sound Co. is currently operating a plant near Salt Lake City in which the new Chemical Construction Corp. technique is applied to cobalt-arsenic sulfide concentrates. In this method the concentrates are leached in a dilute solution of sulfuric acid under air pressure at a high temperature. Near Edmonton, in Alberta, Canada, the Sherritt Gordon Co. is also using the new method in conjunction with its ammoniacal leach process.' National Lead Co., at Fredricktown, Mo., is operating a process similar to that of Howe Sound. In spite of the rapid growth of high temperature-high pressure hydrometallurgical processes, there has been very little work done on fundamental principles involved in this type of process. Conse- quently the literature lacks any significant data in this field. Oxidation of pyrite,3 phalerite,4 galena,5 and recently molybdenite" in alkaline solutions has been reported to some extent. This investigation was initiated, therefore, to broaden the application of high temperature-high pressure hydrometallurgy and also to contribute some insight into the basic mechanisms of oxidation in an aqueous medium under these conditions. In addition to the immediate consequences of these processes much valuable information remains to be learned about fundamental reactions when they are carried out at temperatures and pressures slightly higher than those normally encountered. Leaching of molybdenite by alkaline solutions under oxygen pressure has recently been reported in the Russian literature by E. S. Usataya,8 who found that leaching rate increased with an increase in the pH of the solution—the strongest effects being observed at a pH of 10—and also with an increase in temperature. Usataya also has reported the formation of a protective film on the surface of the molybdenite when the leaching solution was weakly alkaline, neutral, or acidic. He believes that this oxidation process explains the migration of Mo+ + in the oxidation zones of molybdenite ore deposits and the subsequent impoverishment of the ores. Equipment: The high temperature-high pressure reaction unit used in this work was especially designed for kinetic studies of this nature, emphasis being placed on accuracy of measurement and precision of control. As details of the unit's construction and operation have been discussed elsewhere,7 Only basic features and principles of operation will be discussed at this point.

Jan 1, 1957

By Anthony G. Reid

INTRODUCTION At the time of the death of Mao Tse-tung in 1976, China was a major oil producing country with a daily oil flow in the order of 1.735 million barrels. This position had been achieved with minimal assistance from the outside world. Further, only some fifteen years had elapsed since the country's daily oil production capacity had hovered at the barely significant level of one hundred thousand barrels. Why then did the new leaders of China, after this very creditable record of success, suddenly change the direction of the country's drive for future hydrocarbon production? First, by switching much of the emphasis of exploration from onshore to the offshore continental shelf basins, and further by apparently abandoning the philosophy of self reliance calling upon the world's oil industry to share in the task of locating and developing these potential offshore energy reserves. The answer is probably only partly understood by those of us outside China, However, a number of factors exerting an important influence on this decision can be identified. THE MOVE OFFSHORE The new leadership was anxious to rapidly move China into her rightful place amongst the powerful and technologically advanced nations of the world. Modernization became the slogan, specifically modernization on four fronts, agriculture, industry, technology and military with the goal to "catch the west by the year 2000". But how to generate the capital to finance this massive modernization program? The rapid escalation of the price of crude oil following the 1973 Oil Embargo and the continuing apparently insatiable world demand for this now extremely precious primary resource was very clear to all. China, as a major producer, could export crude to help finance the ambitious development programs of the government. To do this, however, would require a very significant in¬crease in present production capacity, as the domestic demand even for China with her relatively low per capita energy consumption, is essentially equal to the current production. Trying to rapidly move the new regime's programs into actions, one can only assume that the planners looked at the success of the petroleum industry over the preceding fifteen years and quickly concluded that this well established curve could be maintained and indeed steepened with an increase in effort. The rapid discovery of a few more Daqing's (China's premier oil field, producing one million barrels a day) would have the country's ambitious modernization goals within reach. Petroleum would At the time of the death of Mao Tse-tung in 1976, China was a major oil producing country with a daily oil flow in the order of 1.735 million barrels. This position had been achieved with minimal assistance from the outside world. Further, only some fifteen years had elapsed since the country's daily oil production capacity had hovered at the barely significant level of one hundred thousand barrels. Why then did the new leaders of China, after this very creditable record of success, suddenly change the direction of the country's drive for future hydrocarbon production? First, by switching much of the emphasis of exploration from onshore to the offshore continental shelf basins, and further by apparently abandoning the philosophy of self reliance calling upon the world's oil industry to share in the task of locating and developing these potential offshore energy reserves. The answer is probably only partly understood by those of us outside China, However, a number of factors exerting an important influence on this decision can be identified. THE MOVE OFFSHORE The new leadership was anxious to rapidly move China into her rightful place amongst the powerful and technologically advanced nations of the world. Modernization became the slogan, specifically modernization on four fronts, agriculture, industry, technology and military with the goal to "catch the west by the year 2000", But how to generate the capital to finance this massive modernization program? The rapid escalation of the price of crude oil following the 1973 Oil Embargo and the continuing apparently insatiable world demand for this now extremely precious primary resource was very clear to all. China, as a major producer, could export crude to help finance the ambitious development programs of the government. To do this, however, would require a very significant increase in present production capacity, as the domestic demand even for China with her relatively low per capita energy consumption, is essentially equal to the current production. Trying to rapidly move the new regime's programs into actions, one can only assume that the planners looked at the success of the petroleum industry over the preceding fifteen years and quickly concluded that this well established curve could be maintained and indeed steepened with an increase in effort. The rapid discovery of a few more Daqing's (China's premier oil field, producing one million barrels a day) would have the country's ambitious modernization goals within reach. Petroleum would be the principal bridge to the bright future. The next decision involved the question of where to look for these vast new reserves. Chinese exploration teams had already looked at most of the onshore sedimentary basins and, while they were the first to admit that there was much yet to do, it was fairly clear to them that the potential for large new accumulations was confined to two areas: the little explored, remote, inhospitable regions of western China, principally Xinkiang Province and the equally unexplored offshore basins of the continental shelf and slope. In both cases China faced a very serious problem. The inhospitable environments were severely straining her petroleum industry's current technological ability to cope, particularly as the government needed rapid results. Thus the pragmatic and, to the foreign oil industry, unexpected decision to invite cooperation with the outside world. The reasons for the initial emphasis on the exploration of the offshore basins with the cooperation of foreign oil companies are again supposition on my part, but probably involved considerations of technical merit, ease of development and delivery to markets together with more sensitive issues such as controling the influence of foreign philosophies and values on the Chinese population by containing most foreign activity to the offshore. So within three years of the death of the great helmsman, China had developed a plan to involve foreign oil companies, both state and private, in a grand plan to rapidly increase the nations oil production. In fact, by this time, the first round of talks had been concluded and the first phase begun, and what a beginning. Some forty eight companies from thirteen countries had signed documents to participate formally in this world scale event. It was far easier to list those companies which did not participate than to list those which did. FOREIGN COMPANY INTEREST Why the rush by the world's oil industry to be involved in China? What was China offering which made everyone so anxious to join in? Again the answer is complex in detail, but principally involved a combination of factors which together caused this virtual stampede. Timing was a major element. Oil Companies, despite an ever increasing take by governments, were beginning to benefit. from the' rapid escalation of crude prices induced by OPEC and were looking for suitable areas to reinvest these funds. Producers

Jan 1, 1982

By Roland de Wit

Conclusions reached in a paper by weertmanl are amplified in a mathematical and graphical way. It is shown that in a stressed crystal a straight dis-location may be in a position of unstable equilibrium with respect to helix development, and how a small perturbation may start the dislocation off on its helical path. Helix development occurs by diffision; bulk diffusion is necessary for development from a screw, but core diffision is sufficient for development from an edge dislocation. For a mixed dislocation helix development can take place by core diffusion if the helix also climbs; a diffusion reversal takes place when the slope of the helix equals the slope of the Burgers vector. The work done on a crystal by the external forces is graphically shown to be consistent with the direction of motion of the dislocation in helix development. Finally a detailed mechanism for tangle formation from helices is presented. In the course of helix development a glide situation may be reached where a segment of each helix loop lies in a slip plane in which it can expand by glide. Thus is it visualized how a helix can deteriorate into a tangle. A paper by weertmanl proposes dislocation-tangle formation by a helical dislocation mechanism. The present paper amplifies Weertman's arguments in a mathematical and graphical way and presents some further ramifications of the proposed model. The importance of dislocation tangles is discussed in Weertman's paper and the references cited therein. The mechanism of their formation is not yet understood. Weertman proposes that in cold-worked crystals conditions exist suitable for the conversion of straight dislocations into helices and subsequently into tangles. Helix formation occurs by a diffusion process and Weertman proposes that at low temperatures only core diffusion is important. The present paper necessarily repeats some of Weertman's work. Since the mathematical development and notation used are slightly different from his, this was thought necessary for clarity. GEOMETRY OF THE HELIX weertman2 has shown that the equilibrium form of any dislocation line is a helix if it is assumed that the energy per unit length (line tension) of the dis- location is constant. For the special case that no external forces act on the dislocation, the helix reduces to a straight line. We shall assume in this paper that the dislocation has a helical form even when it is not in equilibrium. The parametric equation of a helix is, see Fig. l: where a is the radius of the cylinder tangent to the helix, and 270 the pitch of the helix. The pitch is related to v, the number of turns per unit length (along the axis) by the relation: When a = 0 Eq. [I] gives a straight line in the z direction. The growth of a straight dislocation into a helix is now described mathematically by letting a vary from zero to its final value. The tangent to the helix is given by where is the path length along the helix. This gives the direction of t and since its magnitude is unity we must have So that dcp/ds = (a2 +p2)-"'. The curvature of the helix is given by where n = -(cos + sin) is a unit vector normal to the helix. Note that the vectors k and n always point toward the axis of the helix, Fig. 1. FORCE ON THE HELIX The external force which makes the straight dis-

Jan 1, 1963

By H. Groeneveld, C. A. Connally, P. J. Hoenmans, J. J. Justen, W. L. Mason

A miscible displacement pilot using a slug of LPG driven by separator gas was conducted in the Cardiurn reservoir of the Pembina field. The injection pattern was a 10-acre, inverted, isolated five-spot. Upon completion of the LPG-gar phase, an experiment was conducted using a slug of water followed by gas. Calculated performance of the pilot is compared with actual performance. Equations are developed to calculate the distribution of LPG into zones of varying permeability, to estimate the progress of the flood at different times in the various zones and to estimate gas rates after breakthrough. The analysis indicates that permeability stratification was a dominant factor in controlling oil recovery and that oil was completely displaced from the swept pore volume. The results of the pilot indicated that miscible flooding is a practical means of pressure maintenance in this reservoir. The total recovery from the pilot area was good in spite of the early breakthrough of LPG. The effects of stratification were reduced by injecting a slug of water into the partially swept reservoir. INTRODUCTION The Pembina field,' located in Alberta, is the largest oil field in Canada and one of the largest in the North American continent. The reservoir is a stratigraphic trap producing from the Cardium sand. Neither bottom water nor free gas has been found. The recovery of oil by the natural depletion mechanism has been estimated at 12.5 per cent. Pressure maintenance studies of various areas have indicated that the recovery can be increased 21/2 times by water flooding, and a large area of the field is presently under water flood. However, reservoir studies of the North Pembina area indicated that miscible flooding might be competitive with water flooding. A pilot test was conducted to evaluate the performance of a miscible flood. A 10-acre, inverted, isolated, five-spot pattern was selected for the pilot. The pattern area was large enough to minimize wellbore fracturing effects and contained sufficient oil to provide significant working numbers. The performance of each of the four producers could be evaluated individually and compared. In the event of breakthrough in one direction, the effect would be isolated from the other producers. The use of a single injector minimized the volume of LPG required, and, because of the high mobility of gas, one well was sufficient to inject the necessary daily volume to replace the high rate of production. With four producers, the test could be completed in time for results to be evaluated, additional engineering studies to be made and a unit to be formed before the reservoir pressure in the North Pembina area declined below the bubble point. The pilot was located in an area developed on staggered, 80-acre spacing. The injection well was drilled at a regular location, while the four producers were drilled 467-ft north, east, south and west of the injector. Each quadrant and its associated producer were identified according to their direction from the injector— that is, north, east, south or west. The eight surrounding producers on 80-acre spacing were shut in to isolate the pilot area and provide for reservoir pressure observation. The pilot wells were completed using permanent-type completion techniques. After coring, casing was run through the pay section and cemented. Inside 51/2-in. casing, 2 1/2-in. tubing was hung. The wells were perforated opposite the Upper Cardium sand and lightly fractured. Fracturing volumes, rates and pressures were low to minimize the extent of the fractures. The fracturing treatments average 1,000 lb of 20-40 mesh sand in 700 gal of a low fluid-loss sand-carrying agent. Feed rates and wellhead fracturing pressures averaged 5.5 bbl/min at 2,535 psig, respectively. After fracturing, the productivity index was measured in each of the five pilot wells. The average PI of the four producers was 0.41 BOPD/psig drawdown. The measured PI'S were approximately the same as PI'S calculated from core analysis data, indicating that the fracturing treatments were just sufficient to overcome

By J. F. Abel

It can be concluded that rock mechanics instrumentation, geologic mapping, and operations research in combination will produce an accurate estimate of tunnel support requirements for establishing a steel-set load prediction model. This estimate can be used to increase safety and to reduce tunneling costs. Unnecessary supports can be eliminated; overloaded or insufficient supports can be replaced on a more scientific basis than previously possible. Only a limited number of measurements are required to develop a steel set load prediction model. The results of this study can be applied generally; but, every tunnel must be considered as a separate problem. The construction and geologic variables which were found to be significant in the prediction of rock loads in this tunnel were: steel section modulus, set blocking points, percentage of alteration, relative degree of faulting, relative water condition, distance to the nearest fault, and average joint spacing. INTRODUCTION A combined engineering geology and rock mechanics program was performed throughout the Straight Creek tunnel pilot bore in Colorado in order to develop a technique for estimation of steel tunnel support loads. The technique involves the construction of a statistical model from measured steel set loads, geologic and construction factors. The aim of the investigation was to produce a set of charts, based on these factors, which could be used by a trained man equipped with a hand lens and measuring tape, to specify a safe and economical steel size and set spacing. In order to be of practical value the measured parameters had to be rapidly measurable and capable of quantification. It was apparent from the beginning that quantitative values for many of the geologic factors would have to be arbitrary. It was impossible to ascertain in advance which of the readily determi-nable geologic and construction factors significantly affect steel set loading. As the investigation progressed the number of observations was systematically reduced in order to determine the minimum amount of data which would be necessary for a significant mathematical model. This paper presents an analysis of all the variables measured at each instrumented steel set. The statistical significance of the measured variables was determined. On the basis of this determination, a mathematical model was constructed and charts were prepared to select and space the steel tunnel supports at any given point in the tunnel. Once the effect of geologic and construction factors on set loading is sufficiently established, it is possible to exert close control over the selection of steel tunnel support size and spacing. The magnitude of this rock mechanics program can be appreciated when it is known that there were 44 instrumentation stations for which steel set loads were measured. For each of these sets there were three construction variables recorded, and nine geologic parameters determined (Table I). A rough approximation of the cost for both the collection and reduction of the data would be $50,000. This is in addition to the cost of geologic mapping.

Jan 1, 1967

By C. W. Arnold, H. L. Stone, D. L. Luffel

The purpose of this research is to determine (I) the efficiency of small banks of enriched gar driven by methane in displacing oil from a porous medium and (2) the effects of variation in bank size and composition of that efficiency. Most of the experiments were conducted in a sand-packed tube 20-ft long and 1/2-in. in diameter. The hydrocarbon system generally used was methane, butane and decane at 2,500 psia and 160°F. The results of these experiments indicate that, in the regions contacted by the gas, a small bank of an oil-miscible gas driven by methane can displace all of the oil in a piston-like manner. If the enriched gas is of such composition as to remain immiscible with the oil, displacement of oil is less efficient than for the miscible case, and the gas bank travels through the sand with a velocity less than that of the driving gas. These data along with theories discussed imply that smaller banks and less total gas are required when the enriched gas and oil are miscible. INTRODUCTION Widespread application of enriched-gas drive to the recovery of oil rests upon a key factor — the use of limited quantities, or "banks", of enriched gas. At the present time, the value of liquefied petroleum gas or other enriching agents discourages their use in a continuous injection technique, or even in a large bank, except in a few isolated reservoirs. If small banks of enriched gas driven by methane were as effective in displacing oil as is continuous injection, the enriched-gas drive process might be applied to a larger number of reservoirs. Previous research on the mechanics of the enriched-gas drive process reported by Stone and Crurnpl and by Kehn, Pyndus and Gaskell has utilized continuous injection of enriched gas. This work has shown that two types of displacements occur. With gases containing sufficient intermediates. the oil is displaced misciblv and complete recovery is obtained from the regions swept. When gases are used which contain insufficient intermediate hydrocarbon for miscible displacement, oil is displaced immiscibly. In the latter type, selective solution of the intermediate hydrocarbons causes a swelling and reduction in viscosity of the oil and leads to an increased recovery over that obtained by dry-gas (methane) drive. The size of the enriched-gas bank necessary for efficient displacement of oil is determined by those factors which cause deterioration of the bank. A differentiation may be made between those factors which operate on a microscopic scale and those which act on a macroscopic scale. On the smaller scale, the enriched gas mixes in the direction of flow by diffusion and convection with the fluids immediately preceding and following it. On the larger scale, the gas may by-pass the oil by flowing through permeable streaks, by overriding the oil because of density difference, or by fingering because of unfavorable viscosity ratios. In such cases, the enriching material tends to mix with the oil both laterally and in the direction of flow. The increase in effective area available for diffusion and dispersion of the enriching components leads to a faster degradation of the bank and a need for a larger bank than is necessary for those cases in which no by-passing occurs. The effects of such macroscopic factors in the deterioration of enriched-gas banks have been reported in a separate paper by Blackwell, Terry and Rayne. The present study was confined to the factors which operate on the smaller scale, in particular to the behavior of banks of enriched gas in sands uniformly swept by the gas. Experiments were designed to answer the following questions. 1. Can small banks of enriched gas driven by methane be used to secure oil recoveries comparable to those obtained by continuous injection of enriched gas? 2. What is the optimum bank size (the minimum bank size necessary to obtain a recovery comparable to that obtained by continuous injection of the same enriched gas)? 3. How many total pore volumes of gas must be injected to obtain the maximum recovery when the optimum bank size is used? 4. What is the effect of varying the number of enriching components in a gas bank? This report describes the experimental investigations and discusses the results in terms of their significance to reservoir behavior.

By B. E. Eakin, R. T. Ellington

An apparatus and a procedure for determining the viscosity behavior of hydrocarbons at pressures up to 10,000 psia and temperatures between 77 and 400° F are described. The equipment is suitable for measuring viscosity of either the liquid or vapor phases or the fluid above the two-phase envelope for systems exhihiting retrograde phenomena, according no the phase state of the system within these ranges of temperature and pressure. Equations are developed for calculation of viscosity from the experimental measurements, and new data for the viscosities of ethane and propane at 77° F are reported. INTRODUCTION With the advent of higher pressures and temperatures in industrial processes and deep petroleum and natural gas reservoirs, demand has increased for accurate values of physical properties of hydrocarbons under these conditions. Proportionately, more frequent occurrence of natural gas and condensate-type fluids is encountered as fluid hydrocarbons are discovered at greater depths. This increases the importance, to the reservoir engineer, of being able to predict accurately the physical properties of light hydrocarbon systems in the dense-gas and light-liquid phase states. Reliable gas viscosity data are limited primarily to measurements made on pure components near ambient temperature and at low pressures. Few investigations have been reported for high pressures, and except for methane, data on light hydrocarbons are subject to question. This is demonstrated by the large discrepancy between sets of data on the same component reported by different investigators. For mixtures in the dense gas and light liquid regions and for fluids exhibiting retrograde behavior there are very few published experimental data. Viscosity data for methane have been reported by Bicher and Katz,1 Sage and Lacey,12 Comings, et al,3 Golubev,3 and Carr,3 with good agreement among the last three sets of data. Comings, Golubev and Carr utilized capillary tube instruments for which the theory of fluid flow is well established. The theory permits calculation of the viscosity directly from the experi- mental data and dimensions of the instrument alone. Sage and Lacey, and Bicher and Katz used rolling-ball viscometers. The theory of the rolling-ball viscometer has not been completely established, and these instruments presently require calibration by use of fluids of known viscosity behavior before viscosities of test fluids can be measured. To obtain accurate data it is necessary that the rolling-ball viscometers be calibrated by use of fluids of density and viscosity similar to the test fluids, a difficult selection for the gas phase. From the methane data and experimental tests on various natural gases, Carr developed a correlation for predicting the PVT behavior of light natural gases.2,3,4 This correlation was based on data for a very limited composition range; its application to rich gases and condensate fluids is questionable. The object of this investigation is to develop an instrument which can be used to obtain viscosity data at reservoir temperatures and pressures, for rich gases, condensate-type systems above the two-phase envelope and light liquid mixtures. These data will be used in an effort to develop correlations to represent the viscosity behavior of these fluids. APPARATUS In a previous viscosity study Carr2 utilized a modified Rankine capillary viscometer configuration," Fig. 1. In this instrument the gas to be tested is forced through the capillary tube in laminar flow by motion of a mercury pellet in the fall tube, the measured displacement time being that required for the mercury slug to move between the brass timer rings. The viscometer is constructed of glass and mounted in a steel pressure vessel. The test gas pressure in the viscometer is balanced by an inert gas (usually nitrogen) in the vessel. Excellent results have been obtained with instruments of this type, with Carr2 and Comings5 reporting repro-ducibilities of 99.5 to 99.3 per cent and an estimated absolute accuracy of 99 per cent. However, these instruments have limitations which have precluded their use for liquids. The need for maintaining a balance between pressures of the test fluid and inert gas in the viscometer vessel presents operating problems, and requires charging the test fluid to the viscometer very slowly. The principle drawback to the Rankine unit is behavior of the mercury slug which provides the pressure differential across the capillary. When even trace quantities of propane or heavier hydrocarbons are present in the test gas, the mercury tends to subdivide

By R. E. Crockett

MAGNETITE mining and milling in the Eastern States was at capacity during 1940, owing to the heavy industrial, defense, and war demand, coupled temporarily with the almost total stoppage of imports of foreign ores other than those under American ownership. In New York State the active mines were those operated by the Republic Steel Corp. at Mineville and Lyon Mountain. Republic's new concentrating mill at Port Henry, handling the Mineville ores, went into production about the first of April. Other large magnetite deposits in New York are currently being prospected and studied and may be under development in the near future. In New Jersey the Mt. Hope and

Jan 1, 1941

By J. PARKCEH CHANNING

Discussion of the paper of Lewis T. Wright, presented at the New Haven meeting, February, 1909 (Trans., xl., 492 to 495). J. PARKE CHANNING, New York, N. Y. (communication to the Secretary*):-Mr. Wright, in his introductory paragraph, says: " It is commonly believed by metallurgists that in copper-smelting, the copper in the slags, which is irreducible by continued smelting, is retained in the form of 'prills' of matte." On a recent visit to Greenwood, B. C., I was discussing with J. E. McAllister, the general manager of the British Columbia Copper Co., and the former metallurgist of the Tennessee Copper Co., this very question; and he held strongly to the idea that the copper in slag was in two forms-one portion contained in occluded matte and the other as an oxide. He believed that this same rule would apply to the silver in the slag. From my experience I am strongly inclined to agree with Mr. McAllister; and it appears quite reasonable that in furnaces treating oxidized copper-ores, and to a less degree in furnaces treating sulphide ores, there is always bound to be present a certain amount of copper oxide and silver oxide, which will behave like any base and get into the slag as such. We all know that in Arizona, in the early days, when it was customary to produce black copper, because the ores were nearly all oxidized or carbonates, and sulphur was scarce, the slags as a rule carried 2.5 per cent. of copper and seldom ran less than 1.5 per cent. of copper. The economic point was determined by the extra coke necessary to produce the reducing action. In connection with the extra saving in copper, Arthur L. Walker, now professor of metallurgy at Columbia University, and formerly general manager of the Old Dominion Copper Mining Co., at Globe, told me that with coke at $60 per ton it never paid him to make slags containing less than 2.5 per cent. of copper. *Received Oct. 8, 1909.

Feb 1, 1911

By Wesley G. Josephson

THE MINING PROPERTY of the Argonaut Mining Co., Jackson, Calif., is one of the oldest on the Mother Lode. A vein outcropping on a hill in this section could not long elude the eye of the forty-niner, so it was first discovered in 1850. From that time until 1893 the Pioneer mine, as it was then called, limped along under various poorly equipped and financed operators who tried tapping it by trenching and tunneling. Then the Argonaut Mining Co. took over the property and sank the present 65° inclined shaft in the hanging wall of the vein. The mine workings have now reached the 6000-ft. level, which is 5283 ft. vertically below the surface, or just 3 ft. over a mile. The total production of the mine is uncertain, because of lack of early records, but from 1893 to 1932 it is known to have produced in excess of $17,000,000.

Jan 1, 1932

By M. M. Leighton

INASMUCH as the arrangements for the preparation of the review of progress and new developments in the field of industrial minerals (non-metallics) were not made until early December, the writing of this review could not be completed in time to appear in this issue and will, therefore, appear in the February issue. However, we desire to call attention to the steadily increasing importance of this group of mineral substances. The recent book, "Industrial Minerals and Rocks," published by the Institute, lists 47 principal varieties of nonmetallic minerals to which may be added several more of lesser importance. Because of the wide variety of uses to which many of these industrial minerals are put, it is difficult to classify them into categories, but to mention a few examples which indicate the widespread industrial employment of these minerals and their products, one may cite: the use of limestone, gravel, sand, clay products, lime, cement, and gypsum in the construction industry; fluorspar, lime, salt, borax, and sulphur in the chemical industry; diamond, corundum, emery, garnet, flint, quartz sand, tripoli. and diatomite in the abrasive industry; fluorspar, limestone, and magnesite in the metallurgical industry; clay, feldspar, fluorspar, flint, chalk, and limestone in the ceramic industry; and asbestos, gypsum, mica, vermiculite, magnesia, diatomite, and rock wool in the heat, sound and elec-

Jan 1, 1940

By R. S. Dean

JUST as the mineralogical name bauxite has come to include several minerals not known at the time the name was first applied, so the concept of bauxite as the one source of alumina must be enlarged during the war period to include the production of alumina from other, low-grade sources. Speaking in a narrow mineral logical sense, there is no such thing as bauxite, and similarly there is now no one source of alumina, and no one process for its extraction.

Jan 1, 1943