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By J. O. Brittain, E. P. Lautenschlager, F. Felberbauer

This investigation was undertaken to evaluate the effect of a dispersed phase in a iron upon the strain hardening and the stress dependency of dislocation velocity as inferred from the strain-rate sensitivitv. Experiments were made in a-iron specimens with controlled amounts of carbon and/or A12O3. They were tested at various temperatures between 195' and 373 'K under a variety of conditions oj-concentration, strain rate, and quench aging. The resulting yield strength, flow strength, and strain hardening increased with addition of Al2O3. The parameter m, measured from changes in strain rate, was xsed to describe the stress dependency of the dislocation velocity. m was found to increase with additions of A12O3, increasing carbon in solution, and with increasing temperature. When applied to a recent model for yielding based upon dislocation multiplication and velocity characteristics, the values of m alone did not successfully predict yielding for the materials of this investigalion, but had to be adjusted with a consideration of the number of unlocked dislocations nucleated heterogeneously at discontinuities or inclusions. The change of yield strength with Al2O3 Interpar-ticle spacing appeared to obey a theory of Orowan. EVER since the concept of dislocations has been introduced to explain plastic deformation in crystalline materials, the origin of dislocations and the source of the number of dislocations required to account for plastic deformation have been persistent questions. Ruling out the possibility of homogeneous nucleation,' Gilman2 drew attention to the various cases of heterogeneous nucleation as the source of dislocations, whereas Frank and Read3 introduced the Frank-Read source. However, Gil-man found that the Frank-Read sources did not play a dominant role in the deformation of LiF crystals, but that small precipitates are often, if not always, associated with the nucleation of dislocations. In LiF crystals, however, most of the dislocations arose through the multiplication of moving dislocations in a mechanism described by Koehler4 and Orowan,5 Thus, relatively few precipitates could account for a large number of dislocations. A similar observation of dislocation nucleation at inclusions of precipitates was made by Stein and LOW' on Si-Fe crystals. Their crystals contained

Jan 1, 1964

By Stirling Huntley

With the threatened falling off in production of the lighter oil pools of the Tampico embayment in Mexico, a general search of that country for oil-producing regions has resulted in renewed activity in the region of the Isthmus of Tehuantepec, one of the first districts exploited in Mexico. Since the drilling of the first well in the San Cristobal section by the Pearson interests in 1902, drilling has been continuous, except during 1917-1921, when practically all development was stopped by the revolutionary activity. Early in 1921, a drilling campaign was inaugurated for the purpose of testing out the known salt-dome poolfi on the flanks of the salt masses, rather than on their tops where previous tests had been located. On Dec. 7, 1921, the Aguila Co., with which are consolidated the Pearson interests and which has been the only company active in developing this region, unexpectedly drilled into a sand horizon at 3015 ft. with its Conception well No. 18. The hole was unable to handle the production, as a 1400-ft. string of 121/2-in. casing was hanging in the hole, a salt-water horizon drilled through at about 800 ft., was not cemented off, and 3000 ft. of 4-in. drill stem with rotary bit was in the hole. This well's potential capacity was never determined, but it made 7000 bbl. of 25" Bé. oil through the bit and Pin. drill stem, in one of its sporadic flows before sanding up, and thus proved itself capable of the largest potential production of any well on the Isthmus. The well showed salt water before caving and sanding up with the drill stem still in the hole, and will probably never be used for production. Wells Nos. 22 and 23, drilled nearby, have proved disappointments after making good showings of oil. In the spring of 1922, Ixhuatlan wells Nos. 28 and 29, deep tests supposedly on the flank of the known salt cores in that field, went into solid salt; No. 28 at 2250 ft. and No. 29 at 2400 ft. No. 28 was continued in the salt for 1000 ft. before operations were stopped. Later comple-

Jan 1, 1923

By Stirling Huntley

With the threatened falling off in production of the lighter oil pools of the Tampico embayment in Mexico, a general search of that country for oil-producing regions has resulted in renewed activity in the region of the Isthmus of Tehuantepec, one of the first districts exploited in Mexico. Since the drilling of the first well in the San Cristobal section by the Pearson interests in 1902, drilling has been continuous, except during 1917-1921, when practically all development was stopped by the revolutionary activity. Early in 1921, a drilling campaign was inaugurated for the purpose of testing out the known salt-dome poolfi on the flanks of the salt masses, rather than on their tops where previous tests had been located. On Dec. 7, 1921, the Aguila Co., with which are consolidated the Pearson interests and which has been the only company active in developing this region, unexpectedly drilled into a sand horizon at 3015 ft. with its Conception well No. 18. The hole was unable to handle the production, as a 1400-ft. string of 121/2-in. casing was hanging in the hole, a salt-water horizon drilled through at about 800 ft., was not cemented off, and 3000 ft. of 4-in. drill stem with rotary bit was in the hole. This well's potential capacity was never determined, but it made 7000 bbl. of 25" Bé. oil through the bit and Pin. drill stem, in one of its sporadic flows before sanding up, and thus proved itself capable of the largest potential production of any well on the Isthmus. The well showed salt water before caving and sanding up with the drill stem still in the hole, and will probably never be used for production. Wells Nos. 22 and 23, drilled nearby, have proved disappointments after making good showings of oil. In the spring of 1922, Ixhuatlan wells Nos. 28 and 29, deep tests supposedly on the flank of the known salt cores in that field, went into solid salt; No. 28 at 2250 ft. and No. 29 at 2400 ft. No. 28 was continued in the salt for 1000 ft. before operations were stopped. Later comple-

Jan 1, 1923

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 W. B. Gogarty, W. C. Tosch

A new recovery process for producing oil under both secondary and tertiary conditions utilizes the unique properties of micellar solutions (also known as microemulsions, swollen micelles, and soluble oils). These solutions, which displace 100 percent of the oil in the reservoir contacted, can be driven through the reservoir with water and are stable in the presence of reservoir water and rock. Basic components of micellar solutions are surfactant, hydrocarbon and water. They may also contain small amounts of electrolytes and co surfactants such as a1cohol.r. The specific reservoir application dictates the type and concentration of each component. A salient feature of [he process is the capability for mobility control. Micellar solution slug mobility, by way of viscosity control, is made equal to or less than the combined oil and water mobility. Mobility control continues with a mobility buffer that prevents drive water from contacting the micellar solution. Laboratory and field flooding have proven that the process is technically feasible and that surfactant losses by adsorption on porous media are small. Introduction projects are under way to recover the maximum amount of oil under the most favorable economic conditions.' : New techniques are being developed to increase oil recovery,3" Polymer solutions are becoming an important means of controlling mobility in a waterflood. Thermal methods such as in-situ combustion and steam injection are being used in reservoirs containing highly viscous crudes. Surfactant flooding is receiving attention as a method of reducing interfacial tension to increase recovery.*'" Exotic recovery processes have been considered primarily for ' perations. Economics are unfavorable in most cases for tertiary recovery. studies at the Denver Research Center of the Marathon oil CO. have led to a new oil recovery method.* Micellar solutions (sometimes called microemulsions, swollen micelles, and soluble oils) are used to recover oil by miscible-type waterflooding. Basically, these solutions contain surfactant, hydrocarbon, and water. The method can be used in either secondary or tertiary operations. First, thc concept of thc process is considered in terms of the requirements for an effective miscible waterflood ing operation. Next, micellar solution properties are described including structure, composition, and phase behavior with reservoir fluids. Fluid characteristics are then considered as related to mobility control, and, finally, laboratory and field results are presented to illustrate the efficiency of the process. Concept of the Process Unit displacement efficiency and conformance determine the effectiveness of any oil recovery mechanism. In theory, a miscible waterflood should be capable of a 100-percent unit displacement efficiency with a correspondingly high conformance. Requirements for the slug of a miscible waterflood include (1) 100-percent displacement of oil in the reservoir contacted, (2) controllable mobility, (3) the capability of being driven through the reservoir with water, (4) a low unit cost to enhance economics, and (5) the ability to remain stable in the presence of reservoir water and rock. Micellar solutions satisfy requirements for the slug of a miscible waterflood process. Our discovery that these solutions acted as though they were miscible by displacing all fluids in the reservoir and by being displaced by water solved the miscibility problem. Adequate mobility control is possible by variations in solution viscosity through compositional changes. Economic requirements are met since micellar solution costs below $6/bbl appear possible, Mi cellar solutions stabilize surfactant in the presence of reservoir rock and water, thus reducing the importance of the problem of surfactant loss by adsorption. Fig. 1 illustrates schematically how these solutions are used. Operations start with injection of a micellar solution slug that serves as the oil displacing agent. Next, a mobility buffer of either a water-external emulsion or water solution containing polymer (thickened water) is injected to protect the slug from water invasion. Finally, drive water (water used in a regular waterflood) is injected to propel the slug and mobility buffer through the reservoir. Reservoir oil and water are displaced ahead of the slug, and a stabilized oil and water bank develops as shown in Fig. 1. Stabilized bank saturations are independent of original oil and water saturations. This means that, for a particular type of reservoir, the displacement mechanism is the same under secondary and tertiary recovery conditions. Oil is produced first in a secondary operation. For tertiary conditions, water is produced first. Movement of the slug through the reservoir is stabilized by the mobility buffer. An unfavorable mobility ratio usually exists at the interface between the buffer and drive

Jan 1, 1969

By R. H. Jacoby, V. J. Berry

When dry gas is injected into a reservoir containing a volatile crude oil, a significant amount of the reservoir liquid phase may become vaporized. The resultant rich gas phase, when subsequently produced, con-tributes to tank oil production. This contribution assumes greater importance, the more volatile the oil in-olved. Oil recovery may be sub-stantially greater than that predicted by conventional frontal-drive methods, which do not consider the vaporization equilibrium between the reservoir oil phase and the injected gas. A calculation method has been (developed to account for vaporiza-. tion of the reservoir liquid phase during gas-injectiorz operations, and for the tank oil production which results from this factor. Recovery performance calculations are presented for a reservoir containing a highly volatile oil. Tank oil recovery is calculated to be about twice that predicted by the use of the conven-rional frontal-drive equations. In contrastto usual pressure maintenance performance results, in which the gas-oil ratio rises at an increasing rate after gas breakthrough, the pre-dicated gas-oil ratio rises rapidly to about 12,000 scf/bhl and then rises much less rapidly. During gas inje-tion, most of the reservoir liquid phase contacted is evaporated by the dry injection gar. The gas-oil ratio during this period is dependent upon reservoir pressure. The higher the operating pressure, the lower the gas-oil ratio. The predicted behavior i., in accordance with laboratory PVT tests made to .simulate the vaporization behavior. In addition to recovery performance predictions, results of the calculation procedure include complete wellstrearn composition data of value in the design of gasoline plant facilities often used in con-rrction with gas-injection operations. INTRODUCTION In the cycling of gas-condensate reservoirs, dry gas is injected to maintain reservoir pressure during wet gas production and to thereby eliminate or reduce ultimate loss of liquids due to retrograde condensation within the reservoir. Gas injected into crude oil reservoirs has a dual function. It displaces oil to the producing wells and at the same time serves to partially or fully maintain reservoir pressure. Oil shrinkage which would occur upon pressure reduction is thereby minimized or eliminated. Accepted calculation methods are available'= for predicting recovery performance of either gas-condensate reservoirs or crude oil reservoirs which are being subjected to gas injection. In gas-condensate reservoirs, any retrograde liquid formed does not flow, and it is necessary to account only for the vaporization equilibrium between this liquid and the injected gas. Conversely, in normal crude oil reservoirs, both the oil and gas phases flow, but it has not been considered necessary to account for any vaporization of the reservoir liquid which might occur upon contact with the dry injection gas. Recently, high shrinkage reservoir fluids known as "volatile oils" have been found in increasing amounts. These oils are characterized by tank oil gravities above 4.5" API, solution gas-oil ratios above 1,000 scf/bbl, and reservoir volume factors above two. Special techniques have been devised for predicting depletion performance of reservoirs containing such oils.74.5.1; One of the characteristics of reservoirs producing volatile oils is that the reservoir gas phase carries a significant amount of oil which is recoverable as stock-tank liquid. This unusual vaporization be-havior implies that an appreciable amount of reservoir liquid would be vaporized upon contact of the oil with dry injection gas. In a gas-injection operation, tank oil recovery would he obtained not only through frontal displacement of the reservoir liquid by the injected gas, but also through production of the rich gas phase. This means that not only are improved methods needed to predict recovery of such oils from reservoirs undergoing gas injection, but it would also be expected that high oil recoveries might be obtained by such operations. When relatively dry gas is injected in to a volatile oil reservoir, phase equilibrium between the injected gas and the reservoir oil will tend to bc established. Initially the most volatile components, such as propane, the butanes and the pentanes, will account for most of the material transferred from the oil phase to the gas phase. As the partially stripped oil phase is contacted with additional dry injection gas, the heavier intermediate components, such as the hexanes, the heptanes and the octanes, will gradually transfer to the gas phase in increasing amounts. This is because the supply of lighter components in the oil phase dwindles due to the stripping action of the injected gas. This stripping action will usually continue to be effective down

By V. B. Kurfman

The temperature, strain rate, and orientation deDendence of defbrnzation of single-crystal MgAg has been examined. The crystals exhibit a tendency to single glide and little or no hardening at 25°C for many orientations. A much higher hardening rate is observed when multiple glide occurs, such as can be initiated by surface defects. The tendency for easy glide becomes less dependent on surface preparation and orientation as T — 100°C and bars so tested often fail after one-dimensional necking-. At T > 200°C (transition temperature for single-crystal notch sensitivity and poly crystalline ductility) single glide diminishes and two-dirnensionul necking begins. The crystals do not strictly obey a critical resolved shear stress law, but show the influence of {loo) cracks in determining the slip mode. The results are correlated with the difficulty of sciperdzslocation intersection and semibrittle behavior of this compound in single-crystal and poly crystalline form. Comparisons are made with the slip selection mode observed in tungsten, with the reported observations of easy glide in bee metals. and with the mechanical behavior of poly crystalline MgAg. PREVIOUS work on tensile deformation of polycrys-talline MgAgl and bending deformation of single-crystal MgAg2 has shown that the compound is semi-brittle (i.e., notch and grain boundary brittle). If this semibrittleness is supposed to result from the difficulty of multiple glide (associated with the problems of superdislocation intersection) one might expect single crystals deformed in tension to show pronounced single glide and strong orientation dependence of hardening rate. These experiments were done to examine this supposition and to study the tensile deformation of a highly ordered system which may be considered bcc if the difference between the two kinds of atoms is ignored (actual structure: CsC1). EXPERIMENTAL Single-crystal ingots were grown by directional freezing as previously described.' These ingots were sliced into a by a by 2 in, rectangular bars by electric discharge machining, then round tensile bars were conventionally machined to 1/8-in.-diam by 1-in.-long reduced section. The bars were typically tested without an anneal because of the problem of magnesium vapor loss and they were typically tested as mechanically polished. The analyses are within the same limits as those reported earlier; i.e., the average composition for each specimen is within 0.5 at. pct of stoichiometry, while the total range from end to end in a given specimen varies from 0.7 to 1.4 at, pct. There has been no indication in the results of any variation in slip or fracture mode attributable to the composition fluctuations. The slip systems were determined by two-surface analysis of the bars after testing to failure at room temperature. Single glide was so dominant that there was little difficulty in identification of the dominant slip system even though the tensile elongation to failure often approached 7 to 8 pct in room-tempera- ture tests. Elevated-temperature testing was done in a silicone oil bath and low-temperature testing was done in liquid Np or a dry-ice bath. All stress measurements are reported as engineering stress unless otherwise specified, and crosshead travel is used as the strain measurement. RESULTS The tendency toward single glide is best seen in the pictures, Figs. 1, 2, and 3, which depict deformation at fracture as a function of test temperature. While it is possible to find regions of secondary slip by careful microscopy, such regions are very small. The development of a ribbon-shaped configuration from an initially round section bar pulled at 100°C is typical, occurred by single glide, and illustrates the degree to which such glide continues. At temperatures =100°C the bars typically show elongation of 20 to 50 pct by predominently single glide. Despite the large elongation, fracture even at 150°C occurs in a brittle mode, Fig. 2, in the sense that it is an abrupt failure which shows no discernible necking in the second dimension of the bar's cross section (i.e., there is no appreciable action of any slip modes which would decrease the broad dimension of the cross section). Near 200°C the fracture mode changes slightly. Although most of the sample extension is by single glide, after the bar develops the characteristic ribbon shape it begins to neck in the second (i.e., broad) cross-sectional dimension. The bar becomes very thin in the "necked down" region, Fig. 3, and the reduction in area approaches 100 pct. Often there oc-

Jan 1, 1967

By R. H. Kolb

A long term project at Shell Development Co.'s Exploration and Production Research Laboratory has been the improvement of the accuracy and the ease of BHP measurements. As a result of these efforts, two complete and separate systems have now been built for the automatic logging of BHP variations. The first of these is a small-diameter instrument suitable for running through production tubing on a single-conductor well cable. During the development of this instrument, as much emphasis was placed on providing a high degree of usable sensitivity and repeatable accuracy as on obtaining the advantages of surface recording. The second system combines the benefits of automatic, unattended recording with the convenience of a permanently installed Maihak BHP transmitter.' THE CABLE INSTRUMENT For many years the standard instrument for BHP determination has been the wireline-operated Amerada recording pressure gauge or one of several other similar devices. This gauge records on a small clock-driven chart carried within the instrument, and although relatively precise readings from the chart are possible, they are difficult to ob-tain. a Both the maximum recording time and the resolution of the time measurements are limited by chart size, and when a slow clock is required for long tests, the precision of the time measurement is often inadequate. Since it is impossible to determine the data being recorded until the gauge has been returned to the surface, wasted time often results when a test is protracted beyond the necessary time or when it is terminated too soon and must be re-run. Clock stoppage or other malfunctions which would be immediately apparent with surface recording remains undetected with down-hole recording; the test is continued for its full term with a consequent loss in production time. As new uses for subsurface pressure data evolved, the shortcomings of the wireline instrument became increasingly apparent, and the concurrent development of a surface-recording pressure gauge and the associated high-pressure well cable service unit' was undertaken. Description of the Instrument Because of its ready availability and advanced degree of development, the Amerada bourdon-tube element was chosen as the basic pressure-sensing device. This element converts a given pressure into a proportional angular displacement of its output shaft, and a suitable telemetering system was designed to measure accurately the extent of this displacement and to transmit the measurement to the surface and record it. The telemetering system furnishes a digital record printed on paper tape by an adding machine-type printer. The present arrangement provides a resolution of one part in 42,000 over the angular equivalent of full-scale deflection, giving a usable sensitivity of better than 0.0025 per cent of full scale. An additional refinement simultaneously records on the tape the time or the depth of the measurement, also in digital form. When the instrument is placed in operation, an adjustable programer can be set to initiate a read-out cycle automatically at selected time intervals. When subsurface pressures are changing rapidly, readings may be recorded as frequently as once every 10 seconds; when pressures are more nearly stabilized, the period between readings may be extended to as much as 30 minutes. Because the instrument is surface-powered as well as surface-recording, the maximum period of continuous logging is (for all prac. tical purposes) unlimited. The subsurface instrument is a tubular tool, 1 1/4-in. in diameter and 6.5 ft in length, operating on 12,000 ft of conventional 3/16-in. IHO logging cable. The transmitting section, mounted above the bourdon-tube element in place of the regular recording mechanism, contains no fragile vacuum tubes or temperature-sensitive transistors. This unit has been laboratory-tested to 1 0,000 psi and 300°F and has performed dependably during a number of field operations. The down-hole transmitting arrangement can be fitted to any standard Amerada pressure element, regardless of range and with no modification of the element itself. Calibration To obtain a repeatability commensurate with the sensitivity and resolution of the instrument, it was necessary to develop a special calibrating technique. The manufacturers of the Amerada recording pressure gauge claim an accuracy of only 0.25 per cent of full scale, which is a realistic figure for normal calibrating and operating procedures. An exhaustive investigation was made of the errors inherent in the bourdon-tube element, itself, independent

By Ralph Hultgren

IN solid solutions atoms of differing sizes occupy the same crystalline lattice, requiring that some of them be compressed and others expanded. The energy involved has been called misfit strain energy and is an important concept of crystal chemistry. If the atomic sizes and elastic constants of interatomic bonds are known, the misfit energy may be calculated,' provided certain simplifying assumptions are allowable. Usually, isotropic crystals are assumed and interatomic distances are taken to be the statistical average determined from X-ray diffraction. Such calculations yield values of the misfit energy of the order of 1 or 2 kcal per atom in alloys such as Au-Cu at compositions of 50 atomic pct. However, evidence has accumulated in recent times that atoms change their sizes with composition of alloys, implying electronic rearrangement of the bonds. The size changes have been found particularly by application of the X-ray method developed by Warren, Averbach, and Roberts.' Thus, Averbach, Flinn, and Cohen3 determined radii in Au-Cu alloys. Oriani4 showed that these new radii led to a calculated misfit energy in disordered AuCu, which was decreased from the values calculated by the usual theory more than twenty-fold, to only 80 cal per g atom. Thermodynamic calculations from the phase diagram5 also show misfit energy to be no more than a few hundred calories per g atom in this alloy. The question of what electronic rearrangements are possible therefore becomes compelling in estimating misfit energy. In the following pages the results of certain calculations on the AuCu tetragonal superlattice are submitted. Conclusions drawn from these should be applicable in large degree to disordered solid solutions. As in all ordered states, bonding distances in the superlattice are individually known, rather than being merely average distances as found from lattice constants of disordered states. Moreover, only the Au-Au and Cu-Cu distances are strained; the elastic constants of these are known in the elementary state. In the usual calculation it is necessary to assume elastic constants for Au-Cu bonds. Misfit energy has thus been calculable without the need of many simplifying assumptions usually made. It is still assumed that equilibrium bond lengths and elastic properties of the bonds are the same in the alloy as in the pure metals. As previously discussed, this is probably not correct. Also assumed is that the bonds are not affected by strain of neighboring bonds. A calculation of Young's modulus from compressibility data shows this to be far from true; extensive electronic rearrangements take place. It would seem that misfit energy cannot be calculated from elasticity data for the elements. The usual methods may, however, give an upper limit which is often much higher than the true value. The question of electronic rearrangement is, of course, a complex one. Pauling's theory gives a simple, approximate treatment of the relation between type of bond and bond distance. This has been applied with some success to the Au-Cu system, as will be shown in a later section. Misfit Energy in Au-Cu Alloys Hume-Rothery and Raynor6 discuss the Au-CU system as a type example of strain energy. The gold atom is 12.8 pct larger in diameter than the copper atom, near the size factor limit beyond which solid solubility is severely restricted. They therefore consider the misfit energy to be large, a conclusion for which they believe they find evidence in the phase diagram. Gold and copper are completely miscible in the solid state, but the alloy has a minimum melting point at an intermediate composition. From this Hume-Rothery and Raynor conclude that the strain energy is nearly large enough to prevent miscibility; the phase diagram tends toward a eutec-tic type. In Ag-Cu, which has almost identical size relationships, solid miscibility is quite limited; whereas in Au-Ag, where atomic sizes are nearly the same, there is complete miscibility without a minimum in the melting point. From their arguments the heat of formation of Au-Cu would be expected to be endothermic or only slightly exothermic, that of Ag-Cu to be endothermic, and that of Au-Ag to be exothermic. Deviations, from Ve-gard's law of additivity of atomic radii support these conclusions, since Au-Cu and Ag-Cu both have pronounced positive deviations, and Au-Ag has a negative deviation. Nevertheless, Au-Cu alloys form exothermically; indeed, considerably more exothermically than Au-Ag, Table I. Hence, strain energy must be much less important in this case than Hume-Rothery and Raynor have supposed.

Jan 1, 1958

By W. Allen

FOR the past six years gravity surveys have been used for underground prospecting in the copper mines at Bisbee, Ariz. The primary purpose of the surveys has been to reduce the diamond drilling and crosscutting necessary for exploration. Since many of the orebodies are small, and geologic control is not always apparent, any information that will direct the drilling and crosscutting is highly desirable. Because of extensive development and exploration work in the copper mines at Bisbee, it has been possible to cover more than 630,000 ft of crosscuts on 30 levels with the gravity surveys. In the process the gravity procedures have been refined to a high degree. Density Contrast: For a gravity survey to be successful, a sufficient density contrast must exist between the geologic feature sought and surrounding host rocks. Most mineralized areas will provide this contrast if fairly massive bodies are present. In the Bisbee area the entire sequence of formations, except for alluvium, appears to have specific gravities ranging from 2.65 to 2.70. These values have been determined by means of a large number of cut samples and diamond drill cores. As a further check, vertical gravity differences have been used where nonmineralized sections are known to occur.' The only known major gravity disturbances result from mineralization that has increased the density and the voids that have decreased density. The voids are caused by mining operations and by underground water movement that has developed several areas of caverns. Equipment: While not absolutely essential, a small rugged gravity meter, such as the Worden meter, is highly desirable. A tall tripod, about the height of a transit tripod, permits instrument set-ups in deep water and in locations where fallen timber and muck piles make it impossible to use a short tripod. An additional advantage of a tall tripod is that it places the meter in the center of the crosscut, reducing the error caused by the crosscut void. Size and weight are important, since the only satisfactory means of operating the meter underground is to carry it by hand. A backpack can be used in rare instances but is usually a hindrance because of the close station spacing. The operator's ability to move through tight clearances will improve survey coverage, as it is then possible to move through raises and caved areas and to pass mine cars and machinery with a minimum of trouble. Station Control: Gravity stations are normally located every 100 ft along the crosscuts, at each intersection, and in the face of all stub crosscuts. In areas of high gravity relief, or where small anomalies might be expected, stations may be located at 25 or 50-ft intervals. When possible, the stations should be offset to avoid effects of raises or other voids. The gravity stations on a level are tied to one or more base stations, which are usually located at the shaft or near the portal of an adit. The base stations may be part of a gravity control net that extends to each level in the mine as well as to the surface. Such a net extending throughout the potential area of the surveys is highly desirable, as it is then possible to compare all gravity stations on a uniform basis. The stations that are part of the base net should be carefully established by multiple readings and, if necessary, by a least squares adjustment of the loops. In some instances where levels do not have a shaft station, or where access may be blocked by caving, it may be necessary to establish secondary bases at the top and bottom of the raises that are between levels. Under fair conditions 70 to 90 gravity stations can be located and run in 6 hr by a two-man crew. The best field procedures depend on conditions. Reduction of Field Data: Most of the time required to produce a final gravity map is consumed in processing the data. Each meter reading must be corrected for a minimum of five factors that affect the gravity value in addition to the density contrast being sought. These factors are 1) instrumental drift, 2) station elevation, 3) topography, 4) latitude, and 5) regional gravity gradient. Mine openings, such as stopes and raises, will affect the value. However, it is seldom practical to make corrections for these voids. Usually a rotation is made on the field note on the station, and any

Jan 1, 1957

By R. D. Daniels, T. W. Wood

The tensile properties of columbium and Cb-H alloys containing up to 455 ppm H were studied as a function of temperature and strain rate. Hydrogen, introduced into columbium at elevated temperatures, using a thermal -equilibrium technique, embrittled columbium most severely at about —77°C. This elnbrittle ment occurred even at hydrogen concentrations of an order of 20 ppm. At higher temperatures, the hydrogen tolerance of columbium increased in relation to the increased solubility of hydrogen in tile metal. Below this temperature hydrogen tolerance, as determined by ductility and fracture stress, increased slightly. Strain rate had little effect on the tensile results for cross-head speeds over the range 0.002 to 2.0 in. per min. Strain aging during the tensile test appears to explain the ductility mininmum at —77°C. The apparent increase in hydrogen tolerance at lower temperatures is attributed to the low mobility of hyhogen. Experiments were performed in which samples were prestrained in tension at room temperature and tested to failure at —196°C. Results suggest that hydrogetz segregation to preformed crack nuclei can cause subsequent embrittlement even at temperatures where hydrogen mobility is too low to cause embrittlement in a normal tensile test. COLUMBIUM is an example of the class of bcc metals with ductile-brittle transition temperatures sensitive to the presence of interstitial atom contaminants. Hydrogen is one of these embrittling contaminants. The embrittling effect of hydrogen is less potent, perhaps, in columbium than in some of the other bcc refractory metals, but it is still a problem of both theoretical and practical interest. Unlike hydrogen in iron and steels, hydrogen in columbium is exothermically rather than endo-thermically occluded. The embrittlement process in exothermic systems has not been studied as extensively as that in endothermic systems, especially at hydrogen concentrations below the limit of solubility. The purpose of this investigation was to evaluate the embrittlement process in initially pure columbium as a function of hydrogen content, temperature, and strain rate. The Cb-H phase diagram, according to Albrecht et al.,1 is shown in Fig. 1. Columbium reacts exothermically with hydrogen producing a solid solution at concentrations of less than about 250 ppm (parts per million by weight) H at room temperature. At concentrations above the highly temperature-dependent solvus a second phase is formed. Like many similar hydrogen-metal systems,2 his system exhibits a miscibility gap with respect to hydrogen solution. Albrecht found the critical temperature of the miscibility gap to be about 140°C, the critical concentration to be 0.23 atom fraction hydrogen, and the critical pressure to be 0.01 mm Hg. Above 140°C there is a solid solution of increasing lattice constant extending across the phase diagram. Hydrogen concentrations of particular interest in this investigation were those below the limit of solubility in columbium. At hydrogen concentrations above the limit of solubility, columbium will contain the hydrogen-rich second phase and will be brittle under most testing conditions because the hydride generally precipitates as platelets with coincident matrix lattice strains.1'3 At hydrogen concentrations below the limit of solubility, the tensile behavior of columbium is expected to be more sensitive to the interrelationships between hydrogen concentration and mobility and the testing variables such as temperature and strain rate. Literature references to the hydrogen embrittlement of metals, especially ferrous alloys and titanium alloys, are too voluminous to mention. It is only recently, however, that detailed studies of the hydrogen embrittlement of columbium have been undertaken. Wilcox et a1.4 studied the strain rate and temperature dependences of the low-temperature deformation behavior of fine-grained are-melted columbium (1 ppm H) and the effect of hydrogen content (1,9, and 30 ppm H) on the mechanical behavior of columbium at a series of temperatures for a single strain rate. A strain-aging peak was ob-served at about -50°C which was attributed to the presence of hydrogen in the metal. Eustice and carlson5 studied the effect of hydrogen on the ductility of V-Cb alloys at a series of temperatures over the range -196° to 25°C. Pure columbium was embrittled by 20 ppm H which produced a ductility transition at approximately -70°C. Ingram et al.6 studied the effect of oxygen and hydrogen on the tensile properties of columbium and tantalum. A minimum in the notched-to-unnotched tensile ratio of hydrogenated columbium was obtained at about -75°C, but because of the relatively large hydrogen content employed (200 and 390 ppm) the ductility

Jan 1, 1965

By M. I. Sherman, J. D. H. Strickland

USE of a hydrometallurgical approach to the oxidation of sulfide ores and extraction of metals therefrom may have advantages over the more common smelting techniques when a low grade deposit is difficult to concentrate or the subsequent separation of metals, coexisting in the ore, is laborious by any known smelting operation. For economic reasons, the most promising oxidants are either atmospheric oxygen or electric power. The use of oxygen, or air under pressure, has recently been revised. Pyrrhotite has been converted to iron oxide and elementary sulfur' and a variety of sulfides have been treated by Forward and co-workers.2-4 Generally sulfate is the end form of the sulfur but with galena in an acid medium, elementary sulfur can be formed." For economic reasons chlorine and ferric iron salts are about the only possible alternatives to the atmosphere as oxidizing agents for base metal sulfides. If aqueous solutions of chlorine or ferric iron are employed, the reduction products can be oxidized electrolytically in situ and used again, thus acting as catalysts for electric power as oxidant. The use of ferric salts for this purpose is established hydrometallurgical practicea but, although chlorine gas has been employed in the dry state at an elevated temperature, its use in aqueous solution at or near room temperature has not found favor. The reaction of chlorine water with the soluble sulfide ion has been studied by several workers,7-9 and both sulfate and elemental sulfur are found as end products, the latter being favored by the presence of a low concentration of oxidant relative to that of sulfide in solutions of about pH 9 to 10. Of direct bearing on the work in hand are an early American patent" and a recent Austrian patent." The former advocates stirring powdered ore with an aqueous solution of ferric chloride chlorine oxides and chlorine. In the latter it is claimed that both metal and sulfur can be obtained by electrolysis, in a diaphragm cell, of a metal ore slurry in brine. Details in these patents are scant and no data or explanation is given for the mechanism of the reaction which, in the Austrian work, is attributed to the (unlikely) action of nascent chlorine at the anode surface. No mention is made of possible differences in behaviour between various ores. Apparatus A complication encountered when working with chlorine water is that a serious loss of chlorine occurs by gas partitioning unless an enclosed system is used and any air space in the apparatus is kept very small and constant. Arrangements were made, therefore, to take out samples for analysis without letting air into the system to replace the liquid removed. For convenience in studying a heterogeneous reaction the apparatus was so designed that a reproducible controlled stirring rate could be maintained and the ratio of surface area of ore to volume of solution was approximately constant throughout any experiment. The apparatus used is shown in Fig. 1. The ground ore was placed in the horizontal cylindrical vessel, A, of about 1 liter capacity, heated by a constant temperature circulating bath pumping water through the concentric jacket, B. By adding chro-mate to this water, an ultraviolet radiation filter effectively surrounded the reaction vessel, greatly reducing any possible photochemical decomposition of chlorine solutions. Stirring was effected by glass paddles, C, attached by an axle to a magnet which was rotated by another powerful Alnico magnet, D, outside the glass end, this magnet being itself rotated by an electric motor electronically controlled to constant speed. Speed could be varied from about 150 to 900 rpm and was measured and held to within 1 pct of a given value. The end of the reaction vessel remote from the stirring magnet was closed by another one-ended glass cylinder, E, connected by thin polyethylene bellows, F, clamped by screw clamps and watertight rubber gaskets to the main vessel. Through E, a glass electrode and calomel electrode projected into the solution and a hypodermic syringe pierced a small bung and allowed acid or alkaline to be added to maintain a constant pH. By pushing the fully extended bellows until the two cylinders touched, from 50 to 100 ml of solution could be forced out through a sintered disk into the three-way tap system, G, either to waste (for flushing purposes) or up into a 10 ml burette where the solution could subsequently be measured out for analysis. The ore samples were introduced at H, the tube being stoppered by a thermometer of —1 to +52ºC range, graduated to 0.1°C intervals. To prevent ore from being ground in the end bearings of the stirrer these bearings were pro-

Jan 1, 1958

By C. Hays, R. E. Swift, E. G. Kendall

Investigations of the Zr-Pt system, by metallography, incipient melting, and X-ray diffraction, determined the phase relationshifis from 0 to 50 at. pct Pt. Phase fields in the Pt-~ich region were outlined, and three intermetallics (ZrPt, Zr2Pt, and ZrPtd were located. A eutectic between Zr and Zr2Pt, and a eutectoid veaction between Zr and a Zr + Zr2Pt, were established. The maximum solubility of Pt in P Zr was approximately 13.5 wt pct, as opposed to less than 1 wt pct solubility in a Zr. EARLIER work on the Zr-Pt system was limited to an X-ray study on the intermetallic compound, ZrPt3, by H. J. Wallbaum,1 It was reported that ZrPt3 existed at 86.52 wt pct Pt, and had a hexagonal structure, isomorphous with TiNi3. Wallbaum's data revealed the following structural particulars: a = 5.633A, c = 9.21A, and c/a = 1.635A. Other studies allied to Zr-Pt alloys concerned only 1) Pt-rich alloys (0.05 to 5.0 pct Zr) for corrosion resistance,2 2) a Zr-base alloy with 5 pct Pt and 0.124 pct C for oxidation resistance,3 and 3) electroclad-ding of Zr with Pt for in-pile corrosion resistance of Zr to uranyl sulphate. 4 Metallographic, incipient melting, and X-ray diffraction techniques were applied to accurately resolve the phase relationships in the 0 to 50 at. pct (68.2 wt pct) Pt region, and to outline the phase fields in the Pt-rich area. Three intermediate phases: Zr2Pt, ZrPt, and ZrPt3, were also established by the same methods. PROCEDURE Melting stock for this program was of the highest purity obtainable. The Zr was iodide crystal bar with a low hafnium content of about 0.05 wt pct (Westinghouse "Grade 3"). The as-received Zr was treated to remove the surface film of corrosion product that resulted from a standard autoclave grade designation test. Next, the bars were processed to yield material suitable for arc melting and free of contaminants. Sheet platinum metal (Baker and Co. "Grade 2") was used for alloying additions. This material con-

Jan 1, 1962

By Harry V. Welch

Early in the development of the art of metallurgy, it was noted that a distinct difference existed in the character, collection possibility and health hazard of the "smoke" from lead furnaces and those from copper plants. Zinc-plant fumes, although not so detrimental to health, were closely allied in nature to those of the lead works. In Cottrell plants, there are sufficiently distinct differences in operation and amount of construction between those for lead and copper to justify their consideration under separate headings; therefore, while the application of the process at copper-reduction works was covered by the writer some two years ago in the Transactions1,† this discussion will confine itself more distinctly to "fume" collection. General information on the process has been presented in numerous articles and by many authors: Cottre112, Schmidt3, Bradley4, Anderson6, Labbe6, Shiga7, Rathbun8. "Fume" may be defined as material, metal or nonmetal, elemental or compound, evolved as a vapor from a furnacing or chemical reaction and condensing, chilling or reacting within the gas stream to yield a solid form, and in this definition liquid particles are solids in a sense as distinguished from gases or vapors. Such condensed particles are of minute form, on the order of "smoke," and, for example, on the order of a few hundredths of 1 micron (1 micron = 1/25,000 in.) to perhaps 3 microns, with agglomerates, in relatively small proportions of many particles. Metallurgically typical fume products are lead compounds, oxides, carbonates and sulphates; elemental zinc, more commonly encountered as a fume particle of zinc metal with a surrounding "skin" of zinc oxide; arsenic, both metal and oxide and some of its more complex salts such as added sulphates as found in flue dusts; antimony, more particularly its oxide forms; and elemental sulphur, sometimes a troublesome product, in Dwight-Lloyd sintering-plant fumes. These products, particularly the elemental or lower oxide forms, have relatively appreciable vapor pressures at the existing operating temperatures as reported by Welch and Duschak9, Ingold10, Johnstonll, Millar12,13.

Jan 1, 1937

By B. V. P. Rao, H. L. Lovell, G. Simkovich

In the study described here, flotation tests were conducted on pure CaF2, on CaF2 doped at several concentration levels with either NaF or YF3, and on natural fluorite samples containing various amounts of impurities in an effort to extend previous knowledge of the influence of crystalline point imperfections on the flotation properties of solids. The results of these tests showed that although recoveries generally decreased as impurities increased, the differences in recovery were not nearly as striking as those detected in earlier experiments. A number of experimentalists have shown an interest in the way in which crystalline point imperfections affect the flotation properties of solids. As long ago as 1953, Welch hypothesized that it might be possible to control surface imperfections and thereby also control the flotation of solids.' A few years later, in some rather extensive work, Plaksin and his coworkers varied the surface imperfections of a number of compounds by oxidation or reduction processes and found that significant variations in flotation properties resulted.2-4 More recently, Simkovich showed that the recovery of both AgCl and PbS could be markedly varied by adding solid-solution impurities, which acted as doping agents, to these compounds.5 Then Mular studied the flotation of ZnO as a function of the doping agents Al2O3 and Li2O.6 Once again, it was found that these impurities, even in very low concentrations, had profound effects upon flotation recoveries. From an imperfection point of view, the defect structures of the compounds tested previously are as follows:7 PbS — amphoteric semiconductor with a Frenkel-type defect structure in the cation sub-lattice.8 AgCl - ionic conductor-Frenkel type defect structure? ZnO — n-type semiconductor, zinc ion interstitials and quasi-free electrons.10 All of these works undoubtedly bear some relation to the findings that the flotation properties of seemingly identical minerals from different ore deposits often exhibit extreme variation in flotation behavior, i.e., that small amounts of analytically undetectable impurities often have a great influence upon flotation

Jan 1, 1969

By R. E. Shinkosk

This paper outlines the development of a program for increasing the life of woolen bags used for filtering Dwight-Lloyd gases by treating the bags and gases with hydrated lime. Methods and apparatus are described for determining alkalinity of dusts, acidity and breaking strength of bag cloth. Procedure and results, based on several years of operation, are presented. DURING 1939, additional facilities were constructed in the Dwight-Lloyd Blast Furnace and Baghouse departments at the Selby, California, Plant of the American Smelting and Refining Co. In order to handle adequately the increased volume of gases from the resultant increase in production, it was necessary to increase gradually the amount of water used for cooling gases ahead of the sinter machine baghouse. As a result of this increased water cooling, the average bag life dropped from 27 months in 1939 to 14 months in 1941. (Table I). This drop in life meant an increased. bag cost, as well as lower recovery of dust and some curtailment of operation. During 1941, it was found new bags showed as high as 0.3 pct acidity* after two weeks of opera- tion and as much as 2.0 pct acidity after some months of operation. This high acidity was present in spite of the fact that free oxide or relative alkalinity of the unburned dust ran from 5 to 6 pct. In view of these circumstances, a twofold program was started in Nov. 1941.t Part one of this program consisted of vigorously dipping all new bags in a weak lime solution, containing 50 lb of hydrated lime per 50 gal of water. Part two consisted of feeding fine, dry, hydrated lime into the gas stream intake of the sinter baghouse fan. Apparatus for feeding this lime is shown in fig. 1. All baghouse chambers are shaken in rotation about once each hour. On alternate hours, the baghouse operator places 50 lb of hydrated lime (one sack) into the lime feeder, starts feeder and immediately starts the bag shaking machinery. The rate at which lime is fed is set to coincide with the approximate time necessary to shake all sinter bag-house chambers, or about 15 min. It is felt this method of lime addition is most effective for getting lime into the woolen bag fabric. The amount of lime so fed averages about 600 lb per day. The amount of lime fed per day is varied to keep a minimum relative alkalinity of 9 pct in the unburned sinter dust. A daily dust sample is taken for alkalinity by allowing dust to accumulate in a sample pipe over a 24-hr period. This sample pipe, placed in any chamber cellar, is 2 in. in diam, 4 ft long, is sealed on the inner end, and capped on the outer end. It has a 1/2 in. slot cut for 18 in. along the tip end. This slot faces upward and allows the pipe to fill gradually with dust as bags are shaken. Breaking strength of bags has, in most cases, been the deciding factor in bag replacement. Bags that normally test 100 psi breaking strength when new are replaced when they test under 35 lb. The method for determining breaking strength is shown in the description accompanying fig. 2. Since the start of the liming program in 1941, bag life has increased from 14 months to an average of over 23 months, with a consequent material decrease in bag cost per year. Acidity, as per cent sulphuric acid, may be determined by means of a Beckman pH meter as follows: From a piece of bag cloth. which has been thoroughly cleaned of dust, a 5 g sample is weighed on a balance. Cut the sample into fine pieces and place in a 400 cc beaker. Add 100 cc (measured) of distilled water and stir vigorously. Filter on suction funnel, holding cloth pulp in beaker with a stirring rod. Wash cloth sample and filter wash water four additional times, each time with 20 cc distilled water, the last time squeezing cloth pulp over funnel. Discard pulp and rinse funnel and filter paper. Pour wash solution jnto measuring graduate and make up to exactly 300 cc with distilled water. Place into clean 600 cc beaker and measure the pH on meter. The per cent acid in bag cloth is read from the following table:—

Jan 1, 1951

By Rossiter Raymond

JOHN BIRKINBINE was born Nov. 16, 1844, at Reading, Pa., the eldest son of H. P. M. Birkinbine, widely known as a hydraulic engineer. The family removed subsequently to Philadelphia, where, as a young man he established with his father the office now continued by his sons, after more than 60 years. His education was received at public schools, the Friends' High School in Philadelphia, the Hill School at Pottstown, Pa., and the Polytechnic College of Pennsylvania, where his studies were interrupted in 1863-4 by service in the Union Army, which included participation in the battles at and around Gettysburg. Later, he devoted two years to work in a machine shop; and subsequently he became associated with the late P. L. Weimer, under the firm. name of Weimer & Birkinbine, operating the Weimer Machine Works at Lebanon, Pa. Much of his work was in mining, metallurgy, and blast-furnace construction. As manager for the South Mountain Mining & Iron Co. he carried on experiments with various fuels for iron-ore smelting while maintaining the furnace in constant operation. The carefully recorded results obtained were widely published, and are referred to in text-books by other metallurgists as most complete. From his Philadelphia office he was sent to nearly every State, and to Canada and Mexico, for examinations, reports, constructions or improvements in iron-ore mines, blast furnaces, iron works, water supplies, hydraulic development, irrigation projects, etc., and his engineering knowledge was requisitioned by several European corporations. A number of business trips were made to Mexico, beginning with a visit to the Cerro de Mercado at Durango, before railroads were established in that portion of Mexico, to make a critical examination and report on this "Iron Mountain." Later visits covered other localities and engineering problems, familiarizing him with the major part of the iron industry in Mexico. The late disturbed political conditions in that Republic have retarded the probable enlargement, modernization, and improvement of much of the iron and steel industry of Mexico, upon which he investigated and reported for various capitalists on both continents. One interesting subject included in these reports was a proposed electric furnace, to be operated by energy from water power.

Jan 7, 1915

By R. G. Knickerbocker, W. H. Yarroll, P. E. Churchward, J. W. Hunter, J. H. Jacobs

THE present paper records a chapter in the history of the development of an electrolytic manganese industry in the United States.1 A relatively large pilot plant at Boulder City, Nev., for the production of electrolytic manganese was conceived as part of the national defense program to make this country independent of foreign importation of manganese ore. The first authorization, in November 1940, however, was for a plant of only several hundred pounds capacity. Improvements in process and subsequent additions to some sections authorized by subsequent appropriations have enabled the plant to produce as much as 2000 lb. of manganese a day for substantial periods of time. Since in pilot-plant operation frequent changes are made in the flowsheet, the electrolytic manganese plant was constructed so that equipment could be rearranged with a minimum of expense and time. Several different kinds of the various types of equipment were installed for many of the operations, so that the one most suitable for the process might be chosen. Pilot-plant operations were begun in November 1941 and have been continuous except for brief shutdowns for installation of new equipment. More than one-half million pounds of manganese have been produced. The improvements in process, selection of equipment, and operational procedure developed are recorded here. DEVELOPMENT OF THE PROCESS The work of early investigators on the electrolysis of manganese solutions has been reviewed by Shelton.2 Until the method of continuous production of manganese by electrolysis was perfected by Shelton2-4 and coworkers, no practical procedure had been devised. The method as originally developed by the Bureau of Mines will be described here only briefly. The manganese dioxide ore was reduced in a rotating kiln-type furnace at 650°C. in an atmosphere of "city" gas. The calcine was leached with spent electrolyte and enough sulphuric acid to produce a neutral leach solution containing 25 grams manganese per liter as manganese sulphate and 200 grams per liter of ammonium sulphate. Arsenic was removed from the solution by the addition of 0.05 gram iron per liter as ferrous sulphate followed by oxidation

Jan 1, 1944

By Henry Howe

W. E. RUDER, Schenectady, N. Y.-In 1913 I presented a paper before this society on Grain Growth, and at that time it seemed to me that the only explanation for grain growth was that of critical strain. I do not think I published the photographs at the time, but I made some experiments on the effect of stretching sheets of metal. This allowed for fairly accurate determinations of the amount of cold deformation, At the time I worked-with silicon steel because one could see the change in grain growth with the naked eye. I stretched about 10-samples from 0.5 per cent. to 10 per cent., and, after heating to 1,050° C., I found that the maximum grain growth occurred at about 2 ½ per cent. cold deformation. This I designated "the critical strain" for maximum grain growth. About a year ago I talked with Prof. Jeffries, who explained to me his ideas of grain growth. It occurred to me that it would be a very easy thing to check the strain hypothesis against the strain and temperature hypothesis, if we took a certain number of these strips, strained exactly alike and heated to different temperatures; in that case the maximum grain growth ought to appear at a different percentage of deformation for each temperature. These experiments showed that there was, as Mr. Jeffries shows in his present paper, a decrease in germinative temperature with increased cold deformation. The samples were stretched from ½ to 8 per cent. and heated for 10 hr. in hydrogen. Samples were introduced into a furnace previously heated to temperature. A maximum grain growth was obtained at 5 per cent. deformation, when heated to 750° C.; at 2 ½ per cent. when heated to 800' C.; at 1 1/4 per cent., if heated at 950°C.; and at 5/8 per cent.. when heated at 1,100° C. This shows very clearly that the germinative temperature decreases with the increase in cold deformation. The growth was very much more marked, however, at the high temperature, i.e., the grain grew more rapidly and attained a much larger size than at lower temperature. In considering the photographs (Fig. A) those along the lateral edges should be ignored because.

Jan 4, 1917

By C. P. Watson, R. E. Collom

Various chapters already written in the history of development of the North Dome of Kettleman Hills are monotonoysly identical in the one underlying' theme of conservation of oil and gas. Discovered on Oct. 4, 1928, by Milham Exploration Co. with its wildcat Elliot No. 1, the field has been subjected to practically every modern form of production restraint in the name of conservation. The record thus far developed shows that conservation was had for a time, at a price; and that unitiza-tion must be blessed by single ownership or 100 per cent participation to be effective. In fact, incomplete unitization places a heavy handicap upon its participants in the competitive development that follows. Shut-in Agreement of July 25, 1929 Not long after discovery at Kettleman but after the Continental Oil Co. and the Standard Oil Co. had completed several producing wells in the discovery group, came the so-called Shut-in Agreement negotiated at the instance of the Department of the Interior. This agreement became effective July 25, 1929. The fundamental purpose of the agreement was to prevent bringing on production of some 30 wells then being drilled and forestall a flood of Kettleman oil on the market. A cooperative scheme was developed whereby wells in the discovery group would continue to produce. Two of them could not be shut in. Drilling wells would be completed to a water shutoff in top of Temblor and operations suspended. Producing wells would contribute the value of 10 to 25 per cent of their production to the owners of suspended qualifying wells. The percentage rate of drainage contribution was left to a committee or umpire. Some acreage was not placed under the agreement. This same acreage later did not come into the Kettleman Unit Agreement. Several wells on this acreage did not contribute to the drainage fund. The total amount of oil produced during the 17 months of the shut-in agreement, by Milham, Continental and Standard from wells in the discovery group, was 5,297,262.22 bbl. The total amount paid out in "drainage" contributions was $2,046,048.18, representing sales value of 1,266,044.06 bbl. of oil.

Jan 1, 1937