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By C. Williams, D. V. Carter

During 1943 five oil fields and two gas-condensate fields were discovered in the East and East Central Texas district. The New Hope field, discovered by Tide Water-Seaboard in Franklin County, is the most important oil discovery since the Hawkins field in 1940. At the close of the year two oil sands were producing and two additional oil sands were being tested. The gas-condensate fields of Appleby in Nacog-doches County and the Stewards Mill field in Freestone County had only one producing well each. The Carthage field was extended 3 miles north and 4 miles west. Another well that was testing at the year end indicated a probable eastward extension of several miles. The Quitman field, in Wood County, was the most active from the standpoint of drilling operations. Approximately 48 wells were complcted during the year. The second and third most active fields were Hawkins field, Wood County, and Kildare field, Cass County, respectively. Wartime restrictions of material, together with manpower shortage and Federal spacing regulations, reduced the number of oil and gas-well completions from 265 in I942 to 171 in 1943. This represents a drop of 35 percent, or approximately 1/3, enough to replace the 531 producing wells abandoned in the district during the year. No changes were made in the price of crude oil in the district in 1943. The district produced 177,652,940 bbl. of condensate and oil during 1943. This represents an increase of approximately 11 per cent compared with the previous year. The East Texas field, which is the largest and most important field in the district, had an annual production of 128,568,647 bbl. of oil, which is approximately 6.5 per cent more than the previous year, and represents 72 per cent of the district's production of condensate and oil for the year. The district had an estimated basic daily allowable of approximately 509,000 bbl. of oil on Dec. 31, 1943. The entire district produced approximately 30 pcr cent of the state's production for the year 1943. The Hawkins field, Wood County, was operated 271 days during the year and with an average daily production of approximately 52,488 bbl. for the year. This field, which is the second largest in the district, produced 14,224,164 bbl, of oil during the year. Changes in annual production in certain fields in the district can be attributed to their ability to produce at higher rates, the demand, and transportation facilities in the war effort. The East Texas field showed an over-all decrease in reservoir pressure of 8.30 lb. during the year. Indications were that through the first quarter of 1944 the return of salt water to the reservoir was having a beneficial effect. It is hoped that, as more and more water is returned to the reser-

Jan 1, 1944

By D. V. Carter, C. Williams

During 1943 five oil fields and two gas-condensate fields were discovered in the East and East Central Texas district. The New Hope field, discovered by Tide Water-Seaboard in Franklin County, is the most important oil discovery since the Hawkins field in 1940. At the close of the year two oil sands were producing and two additional oil sands were being tested. The gas-condensate fields of Appleby in Nacog-doches County and the Stewards Mill field in Freestone County had only one producing well each. The Carthage field was extended 3 miles north and 4 miles west. Another well that was testing at the year end indicated a probable eastward extension of several miles. The Quitman field, in Wood County, was the most active from the standpoint of drilling operations. Approximately 48 wells were complcted during the year. The second and third most active fields were Hawkins field, Wood County, and Kildare field, Cass County, respectively. Wartime restrictions of material, together with manpower shortage and Federal spacing regulations, reduced the number of oil and gas-well completions from 265 in I942 to 171 in 1943. This represents a drop of 35 percent, or approximately 1/3, enough to replace the 531 producing wells abandoned in the district during the year. No changes were made in the price of crude oil in the district in 1943. The district produced 177,652,940 bbl. of condensate and oil during 1943. This represents an increase of approximately 11 per cent compared with the previous year. The East Texas field, which is the largest and most important field in the district, had an annual production of 128,568,647 bbl. of oil, which is approximately 6.5 per cent more than the previous year, and represents 72 per cent of the district's production of condensate and oil for the year. The district had an estimated basic daily allowable of approximately 509,000 bbl. of oil on Dec. 31, 1943. The entire district produced approximately 30 pcr cent of the state's production for the year 1943. The Hawkins field, Wood County, was operated 271 days during the year and with an average daily production of approximately 52,488 bbl. for the year. This field, which is the second largest in the district, produced 14,224,164 bbl, of oil during the year. Changes in annual production in certain fields in the district can be attributed to their ability to produce at higher rates, the demand, and transportation facilities in the war effort. The East Texas field showed an over-all decrease in reservoir pressure of 8.30 lb. during the year. Indications were that through the first quarter of 1944 the return of salt water to the reservoir was having a beneficial effect. It is hoped that, as more and more water is returned to the reser-

Jan 1, 1944

By Jr. D. C. Williams, D. V. Carter

The four new oil-field discoveries made in the East and East Central Texas districts during 1941 were the East Long Lake field, Anderson County; Pickering field, Shelby County; Pleasant Grove field, Rusk County, and Tri-Cities field, Henderson County. The discovery of oil production in the Pettit lime of the Lower Glen Rose was made in the Groesbeck (Barron) field in Limestone County and the Willow Springs field in Gregg County. Important extensions were made to the Pittsburg field, in Camp County, the Chapel Hill field, in Smith County, and the Hawkins field, in Wood County. The Hawkins field was extended sufficiently to more than double the number of proved surface acres. As usual the East Texas field led the district in the number of completions for the year. The second most active field during the year was the Hawkins field, with 250 new wells completed. The third most active was the Long Lake field, in which 50 wells were completed. Approximately 964 wells were completed in the district during 1941. Production and Probation The district is credited with having produced 163,566,695 bbl. of oil and distillate during the year. This represents a decrease of 4 per cent from the 170,424,685 bbl. of oil and distillate produced during the preceding year. The production of 130,378,620 bbl. of oil and distillate from the East Texas field represents 79.7 per cent of the total production of the district; that is, 6.3 per cent less than the production for the year 1940, The district had an estimated basic daily allowable of 614,982 bbl. of oil on Dec. 31. Approximately 33 per cent of the state's annual production was produced in the district, compared with 34.9 per cent for 1940. Since the majority of the fields in this district are subject to proration, any change in the annual production is attributable largely to changes in proration schedules and number of shutdown days. Fields subject to shutdown days were closed in for 113 days during the year, with the exception of the East Texas field, which was shut down 111 days. An order was promulgated by the Oil and Gas Division of the Texas Railroad Commission for encouraging the disposal of salt water and reservoir-pressure maintenance in the East Texas field. Discoveries Tex Harvey Oil Company'sNo. I S. E. J. Cartmel was completed as the discovery well for the East Long Lake field, Anderson County. Production was found in the Woodbine sand, the horizon from which the Long Lake field produces. The Pickering field, Shelby County, secures its production from the Nacatoch sand, found at an approximate depth of 1510 ft., in A. E. McKiernan's No. I, Pickering Lumbering Co. This field is in an area near the state line in which a number of relatively unimportant and

Jan 1, 1942

By R. W. Gurry

WHEN a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. EXPERIMENTAL PROCEDURE Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;1 it suffices to state here that the carburization lasted about 140 hr. at 760°C. (1760°F.) and 44 hr. at 1110°C. (2030°F.), these periods being long enough-on the basis of the calculations presented later-to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By Jr. D. C. Williams, D. V. Carter

The four new oil-field discoveries made in the East and East Central Texas districts during 1941 were the East Long Lake field, Anderson County; Pickering field, Shelby County; Pleasant Grove field, Rusk County, and Tri-Cities field, Henderson County. The discovery of oil production in the Pettit lime of the Lower Glen Rose was made in the Groesbeck (Barron) field in Limestone County and the Willow Springs field in Gregg County. Important extensions were made to the Pittsburg field, in Camp County, the Chapel Hill field, in Smith County, and the Hawkins field, in Wood County. The Hawkins field was extended sufficiently to more than double the number of proved surface acres. As usual the East Texas field led the district in the number of completions for the year. The second most active field during the year was the Hawkins field, with 250 new wells completed. The third most active was the Long Lake field, in which 50 wells were completed. Approximately 964 wells were completed in the district during 1941. Production and Probation The district is credited with having produced 163,566,695 bbl. of oil and distillate during the year. This represents a decrease of 4 per cent from the 170,424,685 bbl. of oil and distillate produced during the preceding year. The production of 130,378,620 bbl. of oil and distillate from the East Texas field represents 79.7 per cent of the total production of the district; that is, 6.3 per cent less than the production for the year 1940, The district had an estimated basic daily allowable of 614,982 bbl. of oil on Dec. 31. Approximately 33 per cent of the state's annual production was produced in the district, compared with 34.9 per cent for 1940. Since the majority of the fields in this district are subject to proration, any change in the annual production is attributable largely to changes in proration schedules and number of shutdown days. Fields subject to shutdown days were closed in for 113 days during the year, with the exception of the East Texas field, which was shut down 111 days. An order was promulgated by the Oil and Gas Division of the Texas Railroad Commission for encouraging the disposal of salt water and reservoir-pressure maintenance in the East Texas field. Discoveries Tex Harvey Oil Company'sNo. I S. E. J. Cartmel was completed as the discovery well for the East Long Lake field, Anderson County. Production was found in the Woodbine sand, the horizon from which the Long Lake field produces. The Pickering field, Shelby County, secures its production from the Nacatoch sand, found at an approximate depth of 1510 ft., in A. E. McKiernan's No. I, Pickering Lumbering Co. This field is in an area near the state line in which a number of relatively unimportant and

Jan 1, 1942

By R. F. Decker, J. R. Mihalisin

Phase transformations in a series of relatively pure nickel-titanium-aluminum binary and ternary alloys were studied. The purpose was to clarify age-hardening mechanisms, especially in predominantly titanium-hardened compositions. The micro-structures, as determined on a tirne-temperature-transformation basis by light and electron microscopy and X-ray diffraction, were correlated with room temperature and hot hardnesses. The stability of the ? phase under nonequilibrium conditions was shown to be important in this system. MANY of the alloys designed for service in the temperature range of 1200oF (649°C) to 1800°F (980°C) are austenitic iron-.nickel base alloys hardened by titanium and aluminum. The control of high-temperature properties of these alloys has been advanced by the knowledge of microstructures provided by the equilibrium diagrams of Taylor and Floyd1 and Taylor.2, 3 However, there have been notable instances in the predominantly titanium-hardened alloys where the correlation of properties with microstructure and the equilibrium diagrams has been unsuccessful. Mihalisin and carrol14 have noted in electron microscope studies of commercial alloys of this type that a fee phase precipitates and transforms to 71 (hep Ni3Ti) in stress-rupture tests. Bieber5 found that this fee phase remained in nickel-chromium-titanium alloys even when aluminum was excluded. Age hardening in iron-nickel base alloys has been attributed to 71 by Craver, Aggen, and Dyrkacz,6 ? (fee phase based on Ni3Al) by Beattie and Hagel7 and both phases by Lena,8 Yet, on the basis of the nickel-titanium-aluminum equilibrium diagram of Taylor and Floyd shown in Fig. 1, it has been difficult to understand the presence of ? in low aluminum alloys. Furthermore, the characteristic coarse dispersion of 71 has not been commensurate with the marked aging response. Also there have been anomalous grain boundary transformations in the iron-nickel base alloys which have markedly reduced notched stress rupture properties.9 These have been related to boron content and residual cold work. Recently, Golubtsova and Mashkovich,10 Buckle and Manene11 and Bogaryatskii and Tyapkin12 have noted a transition fee Ni3Ti in titanium-hardened nickel-base alloys. It was apparent from the latter studies that a transition phase was important in the nickel-titanium-aluminum system. The purpose of this study was to identify this phase, measure its transformation characteristics and kinetics, and attempt to correlate these findings with age hardening. It was believed that time-temperature-transformation studies, because of their adaptability to transition phases, would be of most value for this investigation. Accordingly, this method of study was undertaken on relatively pure nickel-titanium-aluminum alloys with controlled variations in boron content and residual cold work. EXPERIMENTAL PROCEDURES Compositions were selected from the nickel-titanium-aluminum isothermal section of Taylor and Floyd.' These compositions are plotted in Fig. 1 and were selected to obtain equal aging potential of approximately 15 pet by volume of the equilibrium precipitate. The materials were vacuum melted from

Jan 1, 1961

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1'2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult's law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By Fred W. Stiefel

THIS paper covers the operation and maintenance of Diesel locomotives underground on a portion of the Delaware River Aqueduct.[t] This part of the tunnel is r5 miles long, with shafts 14 ft. in diameter spaced about 5 miles apart. These shafts (2, 2a and 3) are 825 ft., 1551 and 840 ft. deep, respectively. The grade of the tunnel is almost level, except for the 12,100 ft. north of shaft 2, which has a grade of 2.31 per cent. The tunnel is circular, 19 to 19 ft. in diameter, It lies at a depth of 400 ft. below sea level, with a maximum overburden of 2400 feet. The tunnel driving was carried on in six headings, using 15 storage-battery locomotive each of 13 gross tons and having a [inum] speed of 8 miles per hour. The longest haul was 3 miles, which proved to be the maximum distance for which storage-battery locomotives could be employed economically for the amount of material to be moved. One locomotive was used for switching cars at each heading, one for switching cars at the bottom of each shaft and one on the main-line haul from the heading to the shaft. The maximum amount of material hoisted in one shaft from two headings when 104 ft. of tunnel was driven in 24 hr. was 1000 cu. yd., or about 2000 tons of rock in place. The total quantity excavated was 950,000 cu. yd. (1,500,000 tons of rock). The tunnel-lining operations using con¬crete presented a problem of hauling a maximum distance of 5 miles in the tunnel. The concrete-placing equipment had a capacity of about 2000 cu. yd., or 4000 tons in 24 hours. Experience had shown that storage-battery equipment could not handle this quantity of material within the time required at the distance of 5 miles, Trolley-locomotive haulage was considered dangerous and expensive, and would cause interference because transmission equipment would be required. Therefore the performance of Diesel locomotives of 160 hp., with a speed of 18 miles per hour, in comparison with that of other types of locomotives, was studied. CHOICE OF LOCOMOTIVES In deciding upon the type of locomotive to be used for the 5-mile haul, four alternatives were considered, as follows: I. To purchase additional storage-battery locomotives with the necessary batteries over the 6 locomotives and 12 batteries available. 2. To convert the existing battery locomotives to the trolley type. 3. To purchase new trolley locomotives. 4. To purchase Diesel locomotives. PROPOSITION No. I The go-hp. storage-battery locomotives available (each weighing about 12 tons), when hauling a load of 64 tons, with a drawbar pull of about 1900 lb. on a level track, developed a speed of 8 miles per hour and could make five round trips in 8 hr. with a

Jan 1, 1942

By J. W. Borough

THE electrical conductivity of pure copper is markedly decreased by small amounts of impurity in solution. The magnitude of this effect has been very carefully determined by numerous investigators who studied a wide variety of impurity elements. Much of this work is summarized in an excellent review by Pawlek and Reichel.' The case of zinc impurity in copper is an exception to the above in that there has been no well-documented study of the effect using high-purity starting materials. The values for the effect of zinc on conductivity, which are usually taken from unpublished work by Skowronki, indicate that zinc in low concentration has no effect whatever in lowering the conductivity of pure copper. This effect, if true, is unusual since it is generally known that even in lowest concentration, impurities exert an effect on conductivity which is proportional to the amount dissolved. It is more reasonable to suspect that in the original work on the effect of zinc some of the zinc was oxidized out of solution during specimen preparation. The following experi- and calculated d-spacings based on the unit cell dimensions of Baenziger et al. Since the single crystal studies of Baenziger et al. were limited to (hk0) and (hk 1) data, it was not possible to Compare all the intensities of the powder and single crystal patterns. However, the strongest reflections of both studies, the (321) reflection, agree very well when the appropriate multiplicity factor is used. Good agreement was also found in a number of other reflections of lesser intensity. Despite the precautions taken in annealing the U6Fe powder, an appreciable amount of UO, was detected in the powder pattern after heat treatment. The powder pattern reported by Groganoand Clews is given in Table I. Except for the 3.15A line, which is the strongest line of UO,, their pattern, as far as it goes, compares favoEably with the data from this study. Gordon and Kaufmann have reported a diffraction powder pattern purported to be U, Fe but it bears very little resemblance to the patterns of Table I. ments were carried out to redetermine the effect of zinc on conductivity using high-purity starting materials and processing conditions capable of producing oxygen-free alloys. Materials used in the experiment were ASR 99.999 pct Cu and Cumingo 99.999 pct Zn. Four 1 lb melts were prepared with identical procedure in argon atmosphere with crucibles made from Speer No. 580 graphite. The compositions were 0.0, 0.1, 0.3 and 1.0 pct Zn. Standard No. 14 wire (0.064 in. diam) was made from these melts as follows. The 1 pct Zn sample was first reduced 94 pct by cold swaging with five annealing treatments of 800o for 10 min in hydrogen between swagings, and then reduced 94 pct to the

Jan 1, 1962

By E. P. Valby

A method is presented in which the hydrocarbon weight fractional analyses of the well effluents from a true gas-tip-portion well and a true dark-oil-ring well furnish the basic data for determining the properties of any mixture of production from the two sources. The effect of injected gas on these properties can be computed. Comparison of similar properties of a given well effluent to the properties of mixtures of the basic well effluents will give the relative amounts of production from the two sources and injected gas. Presentation of Problem Oil fields having an area of gas-cap, or light-oil production, over the dark-oil area present a problem of increasing gas-oil ratios during the production of an oil well. The use of pressure maintenance in a field such as above, or a cycling project, wherein residue gas from an absorption plant is injected into the reservoir, adds to the problem, because a part of the increased gas-oil ratio may be due to the production of injected gas. The usefulness of a means to determine the amount of injected gas in a well effluent led to the development of a method in which well-effluent analyses of a true gas-cap-portion well and a true dark-oil-ring well furnish the basic data needed to determine whether injected gas of a known composition is present in a given well effluent. Development op Method The method presented herein is based upon the principle that if two fluids, or well effluents, having different properties are mixed in known proportions by weight, • the properties of their mixtures can be computed. Conversely, if these basic data are known, the properties of a mixed well effauent can be used to compute the relative amounts of each type of well effluent in the mixture. A convenient way of making these computations is to have the fractional analyses of the base well effluents and mixtures expressed in weight fractions The mathematical equations expressing the properties of mixtures will be developed for a two-component system consisting of the well effluents from the dark-oil ring and the gas-cap area. The added effect of injected gas, a third component, will also be developed. The following assumptions have been made in developing the method: 1. The gas-cap and dark-oil fluids exist initially in separate portions of the reservoir. 2. The fluids in each portion exist in a single phase at pressures above the saturation pressure for the dark-oil fluid. 3. The composition of each fluid is substantially constant throughout its respective portion of the reservoir. 4. Changes in reservoir pressure and temperature will not change the composition of the fluid entering the well bore. 5. The injected gas displaces original gas-cap fluid 100 per cent. •• 6. AS the injected gas travels through a

Jan 1, 1945

By Cyril Stanley Smith

ON the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1958, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Cavallo3,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold-working restored it. He encountered some samples of brass that could not be rendered magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condition, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitters in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant,9 Honda and Shimizu, 10,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1941

By W. T. Isbell

In the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 1400O to 1500OF and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace were expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. Equipment and Its Uses Degincing Machine.—The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig 1). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.—The treating chamber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1949

record with the Royal Flying Corps was considered a remarkable one, for he was at the front within two months of the date on which he was granted a commission, during which interval he took the prescribed technical course at Oxford, and aviation training at Netheravon and Bristol. On Sept. 14, 1916, he took his first flight over the German lines, when his engine stalled and he had to volplane down, fortunately landing on the French side of the lines. On Sept. 16, he went over the lines with six others, and not returning immediately with the others, was lost. He tried to make for the sea and come back following the course of a river, but when he did descend he found that he was 60 miles west of Paris and 100 miles south of his lines. He flew over to Paris and stayed there for the night, going back to his squadron the next morning. Then on Oct. 4, he was sent up at night for the first time, and in making a landing he passed the flares just as he struck the ground, which put him in total darkness. He struck something and his machine turned a complete somersault, which accident put him in the hospital for ten days. In December, 1916, he left the 21st Squadron and was transferred to the 24th, as the 21st was made an Artillery Squadron and he preferred to remain a fighting scout. In the same month, he was made Acting Flight Commander for about 6 weeks, and about April 3, 1917, his rank of Flight Commander was confirmed. The beginning of May he started to introduce a number of new machines for his squadron, these being of an entirely new type. On May 19, he was up with one of the machines in the evening, practising sharp turns and dives, when the wings suddenly crumpled up and he fell 700 ft., being killed instantly. He was buried in a French Cemetry at Monchy Lagache about 8 miles southeast of Perronne, and about 25 miles east of Amiens. Sergeant Herbert Moore Harbach Herbert Moore Harbach was born in Lebanon, Pa., Apr. 4, 1891, graduated from the Lebanon High School in 1911, and entered State College from which he received his degree of Bachelor of Science in Metallurgical Engineering in 1915. He was employed by the Lackawanna Iron Co., at Buffalo, W. Y., and was later transferred to their Lebanon plant to start up the newly erected benzol plant. He was later made foreman of the coke ovens, which position he held after it was bought by the Bethlehem Steel Co., and until he enlisted in the service of his country in September, 1917. He was stationed at Camp Meade, Md., until the spring of 1918, when he was transferred to the C. W.

Jan 1, 1920

By R. F. Ashton, D. S. Thompson

In reporting results of precipitation hardening experiments, it is customary to include such conditions as solution heat-treatment temperature, specimen size, and quench medium as well as the aging time and temperature. One portion of thermal history that is often overlooked is the effect of the heating rate employed to achieve the aging temperature. It is the intent of this note to demonstrate the importance of the rate of heating to aging temperatures. This work was carried out on the aluminum alloy 7075 aged at 162oC, a temperature commonly used to obtain stress corrosion resistant tempers. A 2 in. thick plate of 7075 was quenched into 24°C water after solution heat-treatment for 2 hr at 470°C. Approximately 13 in. around the periphery of the plate was discarded to minimize quench rate variations, and the remainder was divided into 0.5 by 1.8 by 2.0 in. blocks which were held at room temperature, 24oC, for 4 days. This aging, or incubation period, at room temperature allowed a copious supply of GP-zones to form. Blocks were then heated at various rates to 162oC using the practices shown in Table I. Both single- and two-step aging practices were employed for each heating rate. The single step consisted of heating directly to temperature at the indicated rate while the two-stage practice included an interruption of heating for 7 hr at 107°C. In the case of the two-stage 100°C per min heating rate experiment, the specimens were returned to room temperature after 7 hr at 107°C where they were held for 16 hr be-fore finally heating at this rate to 162°C. This devia-tion in practice is not considered to be significant. Blocks were removed after various times at 162oC, and aging curves were determined from duplicate R. F. ASHTON and D. S. THOMPSON,Member AIME, are Senior Scientists, Metallurgical Research Division, Reynolds Metals Company, Richmond. Va. Manuscript submitted December 2. 1968. IMD Table I. Aging Practices Two-step Single-Step Heating Rate* Aging Aging Heating Method oC per Min A B Programmed Air Oven 0.23 * 0.01 C D Programmed Air Oven 0.93 ? 0.03 E F Air Oven at Temp -10 G H Oil Bath at Temp ˜100 *Heating rate was measured with a thermocouple at the center of a specimen. An average value between the starting temperature and 3°C below the aging temperature is reported for practices E-H. PRACTICES 70 — A B C E and G 50 - 2 4 6 810 20 40 60 HRS.AT 162°C Fig. 1—The influence of processing variables on 7075 aging curves. Fig. 2—7075 aged according to practice H (single-step aged, fast heating rate) for 3 hr. Magnification 100,000 times.

Jan 1, 1970

By A. F. Bertuzzi, M. R. Tek, F. H. Poettmann

A method is presented for predicting pressure drop for two-phase fluid flow in horizontal pipes. A set of 267 experimental measurements randomly sampled from approximately 1,000 measurements from various literature sources was used. Pressure gradients calculated by the procedure developed and compared with the experimental values showed a bias of +0.82 per cent and a standard deviation of 20.8 per cent. The advantatges of this method over other available methods of predicting two-phase flow pressure drop are (a) its comparative simplicity of application, (b) its relative independence of flow patterns, (c) its accuracy, which on the basis of a statistical evaluation predicts pressure drop closer than other available methods, and, (d) its ability to satisfactorily correlate laboratory data from various sources while the correlations from these sources do not appear to agree with one another. The method has been reduced to a simplified graphical procedure, suitable for field use. A two-phase f factor is defined and correlated with parameters involving the flowing gas-liquid mass ratio, a Reynolds number for the gas phase, and a Reynolds number for the liquid phase. The choice of parameters allows the correlation to reduce to the usual f factor plot for the limiting conditions of (111 gas or all liquid. INTRODUCTION The mechanics and characteristics of two-phase flow systems have been of interest throughout the industry for some time. In numerous engineering installations such as pipe lines, chemical reactors, and heat exchangers, two-phase flow conditions are of every day occurrence. In oil production operations it has been desirable, in some cases, to consider transporting gas and oil together in a common pipe from oil field to process plant. The trend toward centrally located stock tank batteries in oil fields has resulted in longer gathering pipelines in which more than one fluid phase is flowing. The increase in the producing capacity of oil wells due to new production tech- niques has created the need for review and re-design of many surface gathering lines for properly handling the increased production. Optimum pipe size for the situations described above has become an important factor. The problem which is of interest here involves the ability to predict the relationship between pressure drop, fluid properties, fluid rates, pipe diameter, and pipe length. Although the literature1,5,10,13,18,19 contains various articles dealing with specific cases of the problem, Lock-hart and Martinelli17 proposed the most general solution. Their method has been later modified by Baker:1 Alves2 demonstrated that different flow patterns are possible for a flow mechanism defined by Martinelli such as gas turbulent, liquid turbulent. Baker explained deviations experienced with Martinelli's correlations on the basis that different flow patterns could exist for the same flow mechanism. Using Martinelli's method of correlatioil, Baker correlated data for each flow pattern for the turbulent-turbulent flow mechanism. Bergelin and Gazley6,7 presented a correlation for predicting gas phase

Jan 1, 1957

By W. C. Ellis, E. S. Greiner

WHEN metallic materials are deformed plastically, the process may be considered as one in which hardening and recovery occur simultaneously. The net hardening is that produced by deformation in the absence of recovery lessened by recovery during and immediately following deformation. Strain hardening takes place through movements of large groups of atoms acting to a degree as an entity. A complex microstress system is developed. Recovery is a diffusive-type process involving single atoms or, at most, only a few atoms in concerted action. This is accompanied by elastic strain relaxation. Recovery is strongly temperature-dependent. The driving energy for the process resides in thermal fluctuations of the atoms augmented by the energy of the stress field producing the deformation, and by that produced by the deformation. At very low temperatures recovery is essentially absent, or very small. At high temperatures in the hot working range, recovery is so rapid that deformation results in no appreciable net hardening. The interplay of strain-hardening and recovery results in differing end structures depending on the temperature and the strain rate of the process. For example, there is a prominent difference in the spacing of the slip markings and in the detail of X-ray diffraction patterns. High temperatures and slow strain rates favor a wide spacing of slip markings and sharp reflections.',' This suggests that change in rate of the recovery concurrent with deformation modifies to a degree the manner of the deformation. Different slip systems may operate. For very slow rates, the mechanism may, as has been suggested, differ from that of "classical slip." In the experimental work that follows the findings will be interpreted from the point of view developed in this section. Recovery and Electrical Conductivity Electrical conductivity is a sensitive indicator of the state of strain in a material3' * and was used in this investigation. The materials studied in wire form were: OFHC copper, a high purity (99.99 pct) and 2s grade aluminum, and grade A nickel. Wire annealed and initially 0.050 in. in diam was drawn through diamond dies in a simple holder maintained at 25", —75°, or — 195°C. Precautions were taken that for each material all conditions of drawing were the same except the temperature. Electrical resistivity was measured for each condition at 20°C. This was done as soon as practical after drawing to minimize possible room temperature recovery. The data for the four materials are plotted in Fig. 1 in terms of the change in resistivity for drawing at the several temperatures. The effect of temperature of drawing on the increase in resistivity is most pronounced for copper. Drawing at 25°C to 80 pct reduction in area increases the resistivity approximately 2 pct; drawing at —195°C to the same reduction increases the resistivity about 6 pct. The increase in resistivity" & in this metal is due to extra scattering of conduction electrons originating in the lack of orderly arrangement of the atoms induced by the deformation process. It has been suggested

Jan 1, 1953

By Robert T. Ault

The nature of fracture in unnotched tensile and notched tensile sheet and round specimens and V -notched and precracked Charpy-type sheet specimens of both wrought stress -relieved and re-crystallized molybdenum was investigated over the temperature range of -78° to 300°C. The sharp rise in fracture stress, for unnotched tensile samples, as the temperature is increased above the brittleness transition temperature (Tb), is found to be a result of an increase in flow stress due to plastic constraint and an increased strain rate which results from the onset of necking at Tb . Quasi-brittle fracture in notched tensile samples is found to occur when the tensile stress at the elastic-plastic interface, beneath the root of the notch, reaches a maximum critical value, which is independent of test temperature over the range from —78° to 25°C, but dependent on microstructure. In the temperature range between 150° and 300°C, unnotched tensile and notched tensile samples alike are found to fracture by a ductile fibrous tearing process which is discontinuous in nature, as a result of the competition between the processes of tearing, through continued plastic flow, and local work hardening. Results from the V-notched and fatigue-cracked Charpy-type impact tests demonstrate that crack initiation is the governing factor in the low-temperature (-78° to 25°C) fracture process for molybdenum. In recent years, there has been considerable interest, and a commensurate number of investigations, concerning the duc tile-to-brittle transition in refractory metals. There has not developed, however, a satisfactory explanation for the uniaxial tensile fracture-stress transition which accompanies the well-known ductility transition. This matter therefore warranted investigation. In a similar manner, the increased importance of notched tensile strength values in evaluating materials and in design criteria requires a better understanding of the factors which control the fracture behavior of notched tensile samples. In a previous investigation1 of the nature of initial yielding and fracture in notched sheet molybdenum at room temperature, it was suggested that plastic constraint was the controlling factor in governing the fracture behavior of notched samples. The final portion of this investigation was concerned with the fracture toughness of molybdenum. Of particular interest was the comparison of effective surface energies for fracture in V-notched samples with fatigue-cracked, Charpy-type samples in order to ascertain the relative importance of the initiation and propagation phases of the fracture process. MATERIALS AND TEST PROCEDURE Sheet tensile, notched tensile, and V-notched Charpy specimens were prepared from 50-mil, stress-relieved molybdenum sheet.* Half of these specimens were vacuum-annealed for 1 hr at 1200°C and 7.5 x l0-5 Torr and furnace-cooled to produce a relatively uniform grain size of 0.30 mm diameter. Round notched and unnotched tensile specimens were prepared from warm-rolled and swaged 5/8-in.-diam bar.* These specimens were vacuum-annealed for 1 hr at 1350°C and 5 x lom5 Torr and furnace-cooled to produce a grain diameter of 0.11 mm. Material analyses in ppm were: C N O H Sheet 290 10 4 1 Bar 50 30 30 2 The unnotched tensile sheet specimens had a 1/4-in. gage width and a 1-in. gage length. The unnotched tensile round specimens had a 9/32-in. gage diameter and a 1-1/4-in. gage length. The sheet and round notch tensile specimens are shown in Fig. 1. All of the notched tensile specimens tested were tandem-notched in order to study the location and mode of fracture initiation. The tandem-notched specimens were carefully machined so that the largest variation in notch depth on a single specimen was 0.001 in. Thus, when fracture occurs, the extent of plastic deformation that exists in the un-fractured notch section is that which exists just prior to fracture. All of the tandem-notched sheet specimens were electrolytic ally polished and chemically etched prior to testing. The V-notched Charpy-type specimens machined from the 50-mil sheet material had the standard dimensions of 2.125 in. long, 0.394 in. deep, and a 0.010-in. root radius. The unnotched tensile and notched tensile tests were conducted over the temperature range of -78° to 300°C, in a 10,000-lb Instron Universal Testing Machine, at a constant crosshead speed of 0.020 in. per min. The V-notched Charpy-type

Jan 1, 1964

By J. L. Huitt, B. B. McGlothlin

The introduction of new fracture propping agents that are brittle but much stronger than sand created the problem of what loading strength is required for a propping agent to be effective in a given formation. It is shown that the load at which the propping agent crushes should exceed the load at which total embedment in the fracture faces is possible. Simple laboratory tests to determine loading strength of the propping agent and embedment in the fracture faces, and use of these data in selecting a propping agent for a given formation, are discussed. INTRODUCTION One of the most important factors in the design of hydraulic fracturing treatments is the selection of a propping agent that can effectively provide the fracture flow capacity needed for stimulation of a well. Sand, once generally accepted as being synonymous with propping agent in hydraulic fracturing, is now recognized as having limited effectiveness in many formations because of its low resistance to crushing. Sand particles are brittle and have relatively low strength. Because of this property, sand particles are crushed in rocks that offer high resistance to the penetration of fracture faces by the proppant particles when the fracture attempts to close under the action of the overburden load. For rocks that offer a high resistance to penetration, deform able particles are more effective propping agents than sand. However, for this same type of rock, a propping agent that does not deform, yet does not crush, is often more effective. Thus, a rigid propping agent with sufficient strength to prevent crushing is desirable. A method for determining the strength required for a rigid propping agent to function effectively in given formations is discussed. BEHAVIOR OF RIGID PROPPANTS AND FRACTURE FACES RELATED STUDIES An early qualitative description of the reaction of propping sand in fractures was given by Hassebroek et al.' In discussing fracturing in deep wells, the authors mentioned that even though propping sand entered the fractures, a high flow capacity did not result due to crushing or embedding of the propping sand. Dehlinger et al.2 in discussing the reaction of propping sand surmised that, because of the hardness of sand particles, deformation occurred in the fracture faces contacting the propping sand. In later studies,3,4 methods of determining the embedment of propping sand in fracture faces of soft rock and the critical load at which propping sand is crushed by the fracture faces in hard rock were discussed. In working with de-formable proppants, Kern et al. considered proppant particles to be deformed into cylindrical disks by action of the overburden and then pressed slightly into the fracture faces by further action of the overburden. Rixie et al.'0 reported on embedment pressure and presented a method of selecting a propping agent for use in given formations. The propping agents included sand, walnut shells and aluminum pellets. All these studies have contributed materially to a better understanding of propping agent behavior; however, the strength of brittle proppants (sand, glass and ceramics) required to result in embedment rather than crushing has not been discussed. This topic will be covered in the ensuing discussion. PROPPANT PARTICLE CRUSHING—-EMBEDMENT For this discussion, a rigid propping agent is considered to be one that is brittle and fails under tensile stress when loaded to a critical value. In an earlier study4 it was shown that the Hertzian4 loading theory could be applied to a spherical brittle propping agent if the propping agent and fracture faces behaved elastically. At the failure of the proppant, the ratio of the load to the square of the diameter of the particle should be constant for a given material combination, or: Lc/dp2=C ............(1) A partial derivation of this equation from proppant and formation properties is included in the Appendix. Should a rigid particle not be crushed as a load is applied, it embeds in the fracture faces. A study3 of particle embedment in fracture surfaces has been published. The embedment can be described by an equation based on Meyer's metal penetration hardness relationships: d1/dp=B 1/2[L/dp2]m/2..........(2) In Eq. 2, B and m are constants that are characteristic of the rock; the significance of the other terms is shown in Fig. 1. A STANDARD DEFINITION FOR PROPPANT LOADING STRENGTH Eq. 1 is useful in appraising propping agent strength," but it is strictly applicable only when the area of contact between a particle and a fracture face (or loading plate)

Jan 1, 1967

By P. M. Robinson, J. S. LI. Leach

The heats of solution oj' indiurrr, tin, lend, nrzd tellurium have been calculated from the measured heat effects when mechanical mixtres of indium and telLuium tin and tellurium, and lead and tellurium were added to liquid bismuth. The results are in good agreement xith publislzed values.s for the separate sollction of each eleltzent in bismuth. The heats oj solution of cadmium and tellurium calculated from the rneasuved heat effects on adding trechanical mixtures of these elements do not ugree zc,itl the published values jbv the separate solution of each element. It is shown that at 623°K Ile interaction between cadmium and tellurium dissolved in liquid bismuth is strong enough to led lo preciPitation of solid CdTc. The heats oj- jor-mation of CdTe at 273" nd 623°K (1)-c crilculated fi-or the measured heat ejlfecls. The calcnlaled az'erage deviation from the Kopp-l\'ez?,zunrz rule fov solid CdTe is less than 0.06 cat per g-atom- C over this lertzperalure range. Tlze importance 0.f these oDserl.ations to the determination of heals of formation hy metal solution calorimetry is considered. LIQUID metal solution calorimetry is a convenient method for determining the heats of formation of solid compounds. In this technique the heat of formation is the difference between the measured heat effects on dissolution of the compounds and of mechanical mixtures of the components in the liquid metal.' The heat of solution of the mechanical mixture may be calculated from the measured heat effect. At infinite dilution of the solutes, this heat of solution is equal to the sum of the heats of solution of the separate components. If the heat of solution of one of the components is known, the value for the other can be derived; if both are known, they may be used to check the accuracy of the calorimetric technique. The heats of formation of the tellurides of cadmium, indium, tin, and lead have recently been measured by metal solution alorimetr. The heats of solution of indium, tin, lead, and tellurium at infinite dilution in liquid bismuth at 623"K, calculated from the measured heat effects on solution of the mechanical mixtures, are in good agreement with the published values. The heats of solution of cadmium and of tellurium calculated from the measured heat effect on solution in bismuth at 623'K of mechanical mixtures of cadmium and tellurium, however, do not agree with values estimated from the literature. 1) EXPERIMENTAL PROCEDURE AND RESULTS The Heats of Solution of Indium, Tin, Lead, and Tellurium in Bismuth. The heat effects were measured when mechanical mixtures corresponding to the compounds In,Te, InTe, In2Te3, In2Te5, SnTe, and PbTe were dissolved in bismuth. The calorimetric procedure and the method of calculation have been described elsewhere.' The heats of solution of the mechanical mixtures were obtained by subtracting the change in heat content per gram-atom of the sample between the addition temperature (273°K) and the bath temperature (623"K), (H623°K - H273°K)S, from the measured heat effects. The calorimeter was calibrated with pure bismuth. The reported values of the measured heat effects are based on (HGoK - ^273oK)Bi = 4.96 kcal per g-atom.3 The measured heat effects are found to be linear functions of the solute concentrations of the bath in the dilute solution range. The values, extrapolated to infinite dilution, are listed in Table I, together with the heats of solution of the mechanical mixtures calculated using the published values of (H 623°K - H273°k)s for indium, tin, lead,3 and tellrium. All the error limits quoted in this work represent the spread of values obtained. The heats of solution in liquid bismuth at 623°K of mechanical mixtures of indium and tellurium in four different proportions were determined. Values of the heats of solution of the two components were then calculated from the resulting four simultaneous equations: The heats of solution at infinite dilution of tin and lead in liquid bismuth at 623°K were calculated from the heats of solution of the mechanical mixtures of tin and tellurium and of lead and tellurium using the heat of solution of tellurium calculated above. These values of the heats of solution are listed in Table I1 together with some published values for comparison.

Jan 1, 1967

By Charles L. Mantell, George Ferment

This investigation determined the jeasibility of current-potential curves as an analytical tool for monitoving manganese electroicinning solutions for metallic impurities. Nine metallic impurities were studied: trickel, cobalt, silver, copper, zinc, molybdenum, catlmiun magnesium, and sodium. The individual effect of each metallic irzplrl,iLy on the standard point-izatiorr was determined for a range of 'concentration. Not all of Ihe impurities affected the polarization curve; correlation between transition current and cotrcetztration of impurity. Molybdenum had an uncorrelated effect on the polarization curie. The effects of binary mixtures of impurities were studied to see if the transition current of the mixture could be predicted. Interactions occurred between impurities which prei'etzted the pvecliction the transition current of tile rrlisLitr.e by additive laws. The polarization curve was shown to be sensitive to metallic impurities which affect the current efficiency of a manganese cell. THE application of current-potential curves in manganese electrowinning is not new but played an important part in the conversion of an inoperative large-scale pilot plant into a continuous comnercial operation.1"" The effects of trace metallic impurities in manganese electrowinning solutions on cathode current-potential curves,5-19 specifically nine impurities (nickel, cobalt, silver, copper, zinc, molybdenum, cadmium, magnesium, and sodium) were studied for a range of concentrations. Cadmium, magnesium, and sodium had no effect. Nickel, cobalt, silver, copper, and zinc yielded a correlation between transition current and concentration of impurity: molybdenum had an uncorrelated effect. Binary mixtures of impurities were studied to de-termine if the transition current could be predicted from the values for the individual constituents. Interactions between impurities prevented the prediction of the transition current of the mixtures by an additive law. The polarization curve was shown to be sensitive to metallic impurities which affected the rurrent efficiency of a manganese cell. The electrowinning of manganese relies upon maintaining a high-purity electrolyte. Purification schemes were developed to remove all of the heavy metals, the magnesium and calcium. Concentration limits have been established for single impurities. With high-purity electrolytes, favorable cell efficiencies are consistently obtained; but with impure solutions there is a reduction in efficiency. With the rapid rise to commercial prominence of electrochemical processes, there has been a lag in developing rapid methods for determining whether an electrolyte is sufficiently pure for efficient electrolysis. The most sensitive test for impurities is the behavior of the electrochemical cell. Impure electrolytes will cause a serious reduction in cell efficiency, and in many cases metal deposition will be prevented or reversed. The effects of impurities are not usually evident until after long periods of electrolysis, resulting in a disruption of the process. A method which could predict the behavior of an electrolyte in terms of cell efficiency prior to reaching the commercial cell is needed. Van Arsdale and Maier," Allmand and Campbell,a1'22 and others attempted to develop an electrochemical process for manganese,"3"29 but all met with some degree of difficulty. Jacobs et a studied the effects of metallic impurities in manganese electrowinning. Plant methods were based on a 2-hr plating in a small electrolytic cell. The final method was based on a 24-hr plating run, performed in a relatively large test cell. Here, current efficiencies were calculated with and without impurities in the electrolyte, and the critical concentration was established as the maximum amount of impurity that the electrolyte could tolerate before there was a serious loss in efficiency. The amount of impurity that could be tolerated decreased as the plating time increased, indicating deposition of the impurity. This test duplicated the conditions of commercial practire, and was sensitive to impurities. Small amounts of impurities significantly affect the hydrogen overvoltage at a metal surface, increasing or decreasing it depending upon the nature of the impurity. ockris established the limit for the onset of poisoning at 10-l moles per liter. The effects of impurities were studied by potential-time curves at a constant current density. The technique did not lend itself to rapid analysis in that several hours were needed to establish stable potential-time curves. Serfass and coworkers3' developed calorimetric and spectrophotometric techniques for analyzing for trace impurities. Our method4'" is based on current-cathode potential curves produced by continuously changing the cell voltage at a programmed rate. Starting with a clean stainless-steel cathode, the cell voltage was initially adjusted to yield zero current: the program was then started and the current was plotted as a function of the cathode potential. Fig. 1 is a typical current-potential curve. In initial region A the hydrogen-evolution reaction predominates and the polarization curve

Jan 1, 1967