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By David Turnbull

IN most reactions involving solids the transformation kinetics may be represented by the combination of two processes-those of nucleation and of growth. For example, Mehl and his coworkers 1,2 in their studies on the transformation of austenite to pearlite in steels have been able to describe the kinetics in terms of the rates of nucleation and of growth. By micrographic examination of their specimens they determined the nucleation rate (rate of appearance of pearlite colonies) as a function of time, of percent transformation, and of temperature. They observed that after an incubation period in which no nuclei are observed, the number of nuclei appearing per unit time per unit of untransformed grain boundary area, increases at an increasng rate with time. When recrystallization rates have been interpreted in terms of rates of nucleation and growth and the rate of nucleation determined, an incubation period followed by an increasing rate of nucleation has also been reported. Among the studies in which this phenomenon has been observed are those of Kornfeld and coworkers3 on cold-drawn aluminum wire, of Anderson and Mehl4 on the recrystallization of aluminum sheet, and of Stanley and Mehl5 on the recrystallization of silicon ferrite sheet. The existence of an incubation period during which no nuclei are observed does not appear to have been reconciled with the generally accepted Volmer-Becker theory of nucleation in condensed systems. This theory ostensibly requires the rate of appearance of nuclei to be independent of time. VOLMER-BECKER THEORY In order to form a stable nucleus of a new phase B in a mother phase A, the molecules or atoms of the mother phase must surmount a free energy barrier whose height is determined by the volume free energy change accompanying the transformation and the energy of the surface separating the two phases. The free energy difference between nuclei of various sizes and the molecules or atoms of the mother phase is plotted schematically in Fig I as a function of the radius of the nucleus r. This free energy difference is plotted for two values of the change of free energy per atom, (fB - fA) accompanying the transformation when the volumes of the two phases are infinite. One of these values of (fa-fA) corresponds to a temperature above the temperature To at which the phases A and B are in equilibrium, and the other to a temperature below To. In order for a nucleus of phase B to be stable at a temperature T2 < To, its radius must be equal to or greater than the critical value r* for which the free energy of formation of the nucleus is a maximum, ?f*. Aggregates of phase B having radii equal to or less than r* will be called embryos. Mehl and Jetter,6 in discussing the kinetics of nucleation in solid systems, suppose that embryos of critical size are formed

Jan 1, 1948

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

By H. H. Stout

In the early fall of 1925, the writer was conducting, in the Ledoux and Co. laboratory, New York, experiments directed toward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various different gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500º to 1600ºF. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode particles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500ºF." Smoot&apos;s reaction, after a few moments considera- tion, was, "It looks perfectly all right to me.&apos;&apos; The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after conferring as to ways and means, decided to go ahead with preliminary laboratory experiments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: 1. Since brittle cathodes were often unintentionally produced, it seemed probable that the laws controlling this type of deposition could be ascertained. 2. We had already proved the gas-cleaning feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia University for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrouilded and heated by a resistance coil 01 Nichrome wire. Broken tough cathodes were used. Experimental Procedure The first run took place March 18, 1926. The resistance wire gave out when temperature of 1000ºF. was obtained. Pressure was immediately applied: perceptible ram movement stopped when 39,000 lb. per sq. in. on the copper was reached, with a maxi-

Jan 1, 1941

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 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;&apos; it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°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 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;&apos; it suffices to state here that the carburization lasted about I40 hr. at 760°C. (1760°F.) and 44 hr. at iiio°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 H. W. III Straley

SOME ten years ago the writer1 made a survey of college catalogues to determine what sort of training geologists were receiving in basic sciences. In the light of this compilation and subsequent experience, he made the statement at the 1939 meeting of the Institute that apparently only in schools offering a curriculum in geological engineering or in the geological option of mining engineering curricula could geologists hope to receive the training advocated by Hubbert.2 In the former study, schools of engineering were excluded because the preparation was known beforehand. The present study aims to consider engineering schools in an effort to determine not only what basic studies are required but what use is made of them in geological courses of the third and fourth years. The present study combined the method of consulting catalogues with a questionnaire. Letters were mailed to officials responsible for supervision of mineral industries curricula requesting information on: (I) the extent to which the engineering preparation of the first two years is actually used in the work of the last two; (2) the extent to which the engineering of the last two years is used in courses in geological engineering or geology; and (3) whether geologists or geological engineers teach descriptively or analytically. Both methods of securing information are open to criticism; the former on the basis of the incomplete information supplied by university catalogues concerning prerequisites and curricula and the latter on the ground that the questions may be phrased poorly or given insufficient consideration by replying officials. Fifty-six questionnaires were mailed and 39 (70 per cent) replies were received. Of the replies, 6 (11.3 per cent) were from colleges of liberal arts unconnected with engineering schools, 11 (20 per cent) were from schools having curricula in geological engineering and 22 (39 per cent) were from departments of mining engineering. The number of replies and their distribution were satisfactory in spite of the receipt of only six from liberal arts colleges. It should be understood that the universities of which the catalogues were examined were not necessarily the same in both compilations. No departments that are admittedly or known to be acting solely as service departments were recorded in the second study. Table I shows that all professional schools require mathematics through calculus, whereas only 7 per cent of the liberal arts curricula expect the same level of preparation; only 73 per cent require trigonometry and 40 per cent college algebra. The proportion of geological engineering curricula requiring differential equations is higher than mining. All of the engineering schools require general and analytical chemistry, whereas only 77 per cent of liberal arts curricula require general and 18 per cent analytical. Twenty-two per cent of the mining and 40 per cent of the geological engineering

Jan 1, 1941

By John M. Sharp

John M. Sharp, Jr. (Assistant Professor of Geology, University of Missouri, Columbia, Mo.)-Geothermal gradient and surface temperature data anomalies are potentially useful tools in mineral exploration, These data, however, may reflect a number of geologic and hydrologic processes as well as the thermophysical properties of the geologic materials. The author presents a relatively simple model which may be of value in mineral exploration. The lack of consideration of other processes, however, limits its usefulness. For instance, because of erosion or sediment deposition over geologic time the land surface must be considered a moving boundary in such a model. Evaluation of this effect coupled with annual surface temperature and thermal conductivity variations can result in temperature profiles such as shown in [Figs. 4 to 7]. These effects and others, such as ground-water movement," must be considered and filtered from the data before proper interpretation is possible. Another assumption which should have been discussed is, why were the observed mean surface temperatures not used for extrapolation of the gradients in [Figs. 4, 6, and 7?] Conductive heat transport responds to the actual boundary (land surface) temperature, not to theoretical temperatures in the absence of perturbations. Benfield presents a theoretical model for calculating perturbations in the geothermal gradient for erosion and sedimentation. The temperature (T) at any time (t) and any depth below the surface (x) is given by [ ] where T is the mean surface temperature, G, the geothermal gradient, v, the rate of erosion (or sedimentation),[ ], the long-term rate of change of T0, and k is the thermal diffusivity of the rock. Using the author&apos;s values and a rate of erosion of 1.54 cm per yr for a period of 10,000 yr, a thermal profile as shown in [Fig. 10] will be generated. A thermal diffusivity of 0.0164 sq cm per sec was used, corresponding to a thermal conductivity of 0.0082 cal per cm per sec per C. In [Fig. 11], a sediment deposition rate of 3.0 cm per yr for a period of 1000 yr was used to generate the subsurface temperature profile. A surface temperature of 24.3°C was used, as specified in [Fig. 9, 7], was set equal to zero for both cases. Superposition on the generated profiles in [Figs. 10 and 11] of the annual surface temperature variation perturbation (which may be calculated in a number of ways) will yield profiles similar to those in [Figs. 4 and 7]. Similar profiles can also be produced by regional ground-water flow. Models like the author&apos;s can be of value in mineral exploration. Other processes, however, which affect surface temperatures and gradients must first be considered, calculated, and filtered from the data if anything but the crudest qualitative interpretation is to be made. Robert C. Edmiston (Author&apos;s reply)-Professor Sharp has raised three objections to my interpretation of the subsurface temperature data I collected at Silver Bell. These are: 1) No correction was made for erosion or sedimentation,

Jan 1, 1977

By J. H. Wernick, S. Geller

A number of new AB, compounds, in which A is a rare earth or yttrium atom and B is Al, Mn, Fe, Co, or Ni, having the cubic MgCu, structure (Laves phase) are reported. In most of the compounds, the interatomic distances are normal; the lanthanide contraction is observed. However, in the compounds CeB2, B = Fe, Co, Ni, Ce appears to have a valence substantially greater than three; in CeAl2, Ce appears to be trivalent. These results are interpreted as vesulting from an energetically more favorable situation for the 4f electron of Ce to be lost to the 3d band of Fe, Co, nnd Ni. Evidence for the existence of homogeneitj! ranges in these compounds is presented. THE purpose of this paper is to report on the crys-tallographic investigations of a large number of new compounds, Table I, with the MgCuz structure (cubic Laves phase). It is a part of a continuing study of the magnetic properties and structures of binary systems involving the rare earths. In a previous paper&apos; some of the magnetic properties of such systems were reported briefly. We have also reported2 a number of compounds of the CusCa type. The compounds were prepared by induction melting in Argon atmosphere of mixtures of stoichiomet-ric amounts of the constituent elements.* For most of the compounds fused alumina or silica crucibles were used as the containing vessel; graphite crucibles were used to prepare CeA12, NdAl2 and TbA12. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis-type Norelco cameras of 114.6 mm diam. The compounds AB2 belong to space group Fd3m-Ol with 8A in a): (000; 01/2 &apos;/2;3) + 000-; b % XA and 16B in dl: (000; oVa %; 3) + 5/87; % %; 7e % Vs\£>. Because the intensities of the reflections on the powder photographs of the different compounds are similar, relative intensities were computed only for DyMnz for CrKa radiation, Table 11. In the calculation of intensities, the Thomas and umeda3 atomic scattering factors, corrected for dispersion,4 were used. The agreement between observed and calculated intensities leaves little doubt that DyMnz has the MgCuz structure. Crystallographic data for the ABz compounds are given in Table JII. Twelve of these compounds have been reported by other authors. A comparison of the published results with our work is given in Table W.* ers of elements of lower purity, to peritectic reactions in some cases, and to the presence of homogeneity ranges in these alloys, so that melting losses would still result in single phase alloys. The possibility of existence of homogeneity ranges in these compounds was investigated systematically only for GdMnz. At room temperature, the solid solution range is between

Jan 1, 1961

By Donald W. Scott, L. A. Roe, B. J. Sweo

INTRODUCTION THIS paper describes the application of ore-dressing methods to the reclamation of milled frit from over-spray, or waste, porcelain enamel. Frit is the name given by enamelers to a granulated glass produced by the smelting and subsequent water quenching of various ingredients capable of forming a glass, usually including a compound to produce opacity. It is the major component of porcelain enamel, and normally commands a price ranging from 7 to 12 cents a pound. In the preparation of a white enamel slip, usually 6 or 7 parts of clay, 2 parts of opacifier, small amounts of electrolytes, in some cases inorganic color stabilizers and organic dyes, and 35 parts of water are added to loo parts of frit; the mixture then is milled to a fineness of the order of 92 to 95 pct through a 200-mesh sieve. The frit forms the base of the enamel; the opacifier imparts opacity or reflectance; the clay suspends the frit while in slip form and serves as a binder&apos; in bisque form (dry and unfired); and the electrolytes control the workability. Spraying is used commercially, in many cases, to apply the finish coat of enamel to the ware, prior to drying and firing. In the spraying operation, only about 50 pct, by dry weight, of the enamel slip adheres to the surface of the ware, the remainder forms the over-spray. From 1/2 to 2/3 of the overspray goes up the flue where it is lost or recovered, depending on whether the plant is equipped with a dust-collecting installation; the coarser portion of the overspray is collected in the spray booth. The former product is termed flue reclaim enamel, and the latter booth reclaim enamel. Although the spraying operation is done in specially constructed booths, which are partially or completely enclosed, it is extremely difficult to keep out contaminating dirt, which joins the reclaim. Some present-day large enameling plants use 20 tons of frit a day, of which 10 tons go into reclaim with a potential value of $1400 to $2400. When two-coat finish enamels were common, the reclaim was used satisfactorily for the undercoat, but the relatively recent advent of one-coat finish enamels prevented use of the reclaim because, even when blended with first-run enamels, it gave dirty finishes with poor gloss. It was thought that the pitting and specking encountered with reclaimed enamels were caused by the contaminating dirt, and that the poor gloss was caused, primarily, by the high clay content; more clay usually was added to give proper suspension properties to the slip when the reclaim was used. A clay content in excess of about 10 pct usually imparted refractoriness to porcelain enamels. Present-day one-coat porcelain enamels must combine high gloss and opacity with freedom from surface defects. Methods of beneficiating the over-spray,

Jan 1, 1947

By N. A. Tiner

A study was made of the effects of temperature, type of loading, and electric polarization on the fracturing behavior of copper and zinc coated with mercury. Copper showed an em-brittlement only in cyclic loading, whereas zinc showed an em-brittlenzent in both static and cyclic loading. The embrittle-ment of zinc in static loading was prevented by sub-zero cooling to a temperatzcre of about -70°F. The emhrittlement of both metals was sliglztly reduced by cathodic polarization of mercury. The basic processes involved in fracturing were discussed in the light of these observations. When a solid metal is in contact with certain liquid metals possessing high wetting characteristics, a weakening effect is produced, and the solid metal fractures in brittle manner at a relatively low stress. This lowering of the fracture stress generally is considered different from the stress cracking caused by a corrosive liquid environment and is attributed to the lowering of the solid-liquid interface tension at the grain boundaries.1-4 The purpose of this paper is to describe a number of observations on the special features of fracturing of copper and zinc coated with a liquid mercury film, and to analyze the basic processes involved in fracturing in the light of these observations. EXPERIMENTAL OBSERVATIONS I) Effect of Type of Loading—The evidence appears to indicate that in static loading, metals usually fracture by the initiation of microcracks in the interior preferentially at the grain boundaries or at the intersection of slip bands.&apos; In cyclic loading, cracks develop on the surface within the active slip zones, and gradually propagate with increasing num- ber of cycles.6&apos;7 Because of this difference in the manner of initiation of cracks, a series of bare and mercury coated copper and zinc specimens was subjected to static and cyclic loading, and their fracturing behavior was examined. The specimens were machined to 0.25 in. in diam and 1 in. in length from a high-purity commercial bar stock, and annealed at an appropriate temperature. Mercury was applied to the surface of the specimens by rubbing with cotton wool soaked in a saturated solution of HgCl2 or by etching with a dilute solution of HC1 and rubbing with purified mercury and by washing in water. The static tension load-extension curves were obtained by means of a Riele Screw Power Universal Testing Machine. The room-temperature load-extension curves for copper and zinc are shown in Fig. 1. The deformation behavior of copper, as judged from the general configuration of the load-extension curve, was not affected by mercury coating. The maximum load to fracture and the elongation at the maximum load were practically the same for both specimens. The mercury coated copper, however, showed somewhat less localized necking and had smaller reduction of area than the uncoated metal. The behavior of mercury coated zinc was radically different from the behavior of uncoated metal. The load-extension curves were the same at the

Jan 1, 1962

By J. M. De La Garza Cárdenas

The total production of oil in Mexico in 1942 was 34,715,547 bbl.; that is, 8,179,254 bbl. less than the amount produced in 1941. The daily average for 1942 was 95,111 bbl., while that for 1941 was I17,520 barrels. The reduction of 22,409 bbl. per day in production was due to a decrease in exports because of the scarcity of tankers. This reduction has affected principally the Northern and Southern districts of the Tampico area; in December the Northern district (Panuco) was producing less than zoo0 bbl. per day with 445 wells shut down and the Southern district (GolJen Lane) less than $000 bbl. per day with 140 wells shut down. Drilling.—During the year 14 wells were drilled in Mexico, of which five were productive. Seven dry holes were drilled in Ebano, Tampico Northern district, in search for new producing fractures; plans are being made to explore this area by means of resistivity measurements. Three producing wells were completed in Poza Rica. Drilling in this important field will continue during 1943 to determine its extension to the west. In the Isthmus of Tehuantepec no wells were completed. Two gas wells were completed in northeastern Mexico. Wildcats.-—Two wildcat wells were completed during the year, to test the extension of the Golden Lane to the south; both were unproductive. In the Isthmus a deeper sand was found in the El Plan field* This discovery has made an important increase in the reserves in this field and will allow an increase in the production of the area during 1943. In December, three exploration wells were being drilled, two in the Tampico area and one in the Isthmus. Operating Technology.— Satisfactory progress has been made in Mexico in the application of petroleum engineering to the development and operation of the oil fields. Mud control is now an established practice and has lessened the number of fishing jobs and has allowed more open hole to be carried than formerly was possible. During 1942 the first effective use was made of determinations of bottom-hole pressure, and other modern production practices such as gun-perforating and squeeze-cementing are being introduced. Plans for 1943 The oil production during 1943 is expected to be slightly larger than that of 1942, especially if tankers are available for exporting crude and refined products. The Government proposes to increase exploration and drilling activities to increase the reserves and potential production of the country; about 50 wells will be drilled during the year, including wildcat wells in northeastern Mexico, Tampico and Isthmus areas and exploitation wells in the Ebano-Panuco, Poza Rica, El Plan and Cuichapa fields. Acknowledgment Mr. A. Barnetche, of the Production Department, "Petr6leos Mexicanos," assisted the writer in the preparation of the statistical data.

Jan 1, 1943

By J. M. De La Garza Cárdenas

The total production of oil in Mexico in 1942 was 34,715,547 bbl.; that is, 8,179,254 bbl. less than the amount produced in 1941. The daily average for 1942 was 95,111 bbl., while that for 1941 was I17,520 barrels. The reduction of 22,409 bbl. per day in production was due to a decrease in exports because of the scarcity of tankers. This reduction has affected principally the Northern and Southern districts of the Tampico area; in December the Northern district (Panuco) was producing less than zoo0 bbl. per day with 445 wells shut down and the Southern district (GolJen Lane) less than $000 bbl. per day with 140 wells shut down. Drilling.—During the year 14 wells were drilled in Mexico, of which five were productive. Seven dry holes were drilled in Ebano, Tampico Northern district, in search for new producing fractures; plans are being made to explore this area by means of resistivity measurements. Three producing wells were completed in Poza Rica. Drilling in this important field will continue during 1943 to determine its extension to the west. In the Isthmus of Tehuantepec no wells were completed. Two gas wells were completed in northeastern Mexico. Wildcats.-—Two wildcat wells were completed during the year, to test the extension of the Golden Lane to the south; both were unproductive. In the Isthmus a deeper sand was found in the El Plan field* This discovery has made an important increase in the reserves in this field and will allow an increase in the production of the area during 1943. In December, three exploration wells were being drilled, two in the Tampico area and one in the Isthmus. Operating Technology.— Satisfactory progress has been made in Mexico in the application of petroleum engineering to the development and operation of the oil fields. Mud control is now an established practice and has lessened the number of fishing jobs and has allowed more open hole to be carried than formerly was possible. During 1942 the first effective use was made of determinations of bottom-hole pressure, and other modern production practices such as gun-perforating and squeeze-cementing are being introduced. Plans for 1943 The oil production during 1943 is expected to be slightly larger than that of 1942, especially if tankers are available for exporting crude and refined products. The Government proposes to increase exploration and drilling activities to increase the reserves and potential production of the country; about 50 wells will be drilled during the year, including wildcat wells in northeastern Mexico, Tampico and Isthmus areas and exploitation wells in the Ebano-Panuco, Poza Rica, El Plan and Cuichapa fields. Acknowledgment Mr. A. Barnetche, of the Production Department, "Petr6leos Mexicanos," assisted the writer in the preparation of the statistical data.

Jan 1, 1943

By E. S. Machlin, C. W. Chen

THIS investigation is concerned with the origin of the intercrystalline voids and cracks formed in metals and alloys subjected to stress at elevated temperature. There have been many suggestions in the recent literature relating to this problem. Greenwood&apos; suggested that the voids may be produced by vacancy condensation. Zener has stated that shear-stress relaxation across grain boundaries could initiate high tensile stresses at the regions blocking grain boundary slip and thereby cause the formation of cracks. Chang and Grant3 have described the formation of cracks at grain boundary triple points and have experimentally verified Zener&apos;s mechanism for the grain boundary regions in the vicinity of a triple point. Subsequent to the completion of this investigation, Gifkins4 developed a model which made use of Stroh&apos;s5 mechanism of fracturing to produce sub-microscopic fractures that subsequently grow by grain boundary slip. Chen and Machlin,6 in answer to Gifkins, described a model deduced from the present investigation, in which grain boundary slip provides both the stress to fracture at grain boundary jogs and the deformation required to separate fractured jog surfaces. The possibility of gas condensation to form intercrystalline voids and cracks is eliminated as a basic mechanism because such voids and cracks are developed in vacuum melted material containing minute amounts, if any, of gaseous impurities. In a theoretical evaluation of this problem, Machlin7 concluded that void nucleation by vacancy condensation during creep-rupture is improbable but that vacancy condensation on supercritical sized voids to produce growth is probable. This investigation was begun to evaluate the suggested mechanisms for intercrystalline fracture. In particular, in order to correlate vacancy supersaturation ratios produced in creep with those determined by Bal-luffi and Seigle8 as critical for , the nucleation of voids, specimens were obtained from the same heat of brass as used by the latter authors, through the courtesy of Dr. Seigle. The experiments conducted in this investigation fall into the following categories: 1) Brass—observation of voids produced under a variety of conditions, including creep under compression, to evaluate the mechanisms of void nucleation and growth. 2) Bicrystal experiments to check the mechanism of void nucleation deduced in this investigation. 3) Morphology of intercrystalline voids produced in a variety of metals. Each set of experiments will be described and discussed separately. Experimental Techniques A special creep-rupture test rack was constructed which made it possible to apply the stress to the specimen in a controlled atmosphere of inert gas, reducing gas, or vacuum. All the creep-rupture tests on a-brass (30 pct Zn) were conducted in nitrogen under a pressure slightly above atmospheric. Either dead weight loading or constant elongation rate loading could be applied with the load measured by means of a strain gage dynamometer. In order to obtain a coarse-grained crystal structure stable at

Jan 1, 1958

By James W. Halley

&apos; FINE-GRAINED " steels have been standard products for many years. This paper describes an investigation of the effects of some of the more common grain-growth; inhibitors used to produce these steels. The properties, response to heat-treatment, and the deoxidation practice necessary to produce "fine-grained" steels have been the subjects of numerous papers. It has been shown that a substantial quantity of&apos; aluminum is necessary to produce this type of steel, and it has been indicated that titanium and zirconium produce a similar result. For some time there was a lively argument between those who felt that aluminum refined the grain and those who felt that aluminum oxide was the effective agent. This argument subsided with an apparent victory for those promoting aluminum oxide. Most of the work on grain size has divided steels into two broad classifications based upon McQuaid and Ehn&apos;s original carburizing test at 1700°F. or some similar test at this temperature. If the steel coarsened at this temperature, it was coarse grained, while if it did not it was fine grained. Quantitative data concerning how much a certain amount of aluminum raised the coarsening temperature and affected the properties, all other factors being constant, are very meager. Similar information regarding titanium and zirconium is practically nonexistent. The published information on aluminum yields some quantitative information. Epstein, Nead and Washburn&apos; gave the first quantitative information on the amount of aluminum necessary to prevent grain growth at 1700°F. They showed that the addition of a pound to a pound and a half of aluminum per ton (0.05 to 0.075 per cent) would assure steel that would not .coarsen during a McQuaid-Ehn test at 1700°F. Herty, McBride and Hough2 reported that a steel containing 0.020 per cent acid-soluble aluminum coarsened between 1742° and 1832°F., while steels containing 0.016 per cent and 0.017 per cent acid-soluble aluminum coarsened between 1652~ and 1742°F. compared with similar aluminum-free steels that started to coarsen at 1580°F. Herty3 also showed a marked improvement in low-temperature notched impact resistance with increasing acid-soluble aluminum up to 0.030 per cent. McQuaid4 compared the coarsening of steels containing 0.011 to 0.204 per cent total aluminum and found a maximum coarsening temperature at 0.098 per cent aluminum. He had no samples between 0.015 and 0.098 per cent aluminum. Houdrement5 found a marked decrease in coarsening temperature with aluminum contents above 0.50 per cent. Kinzel, Crafts and Egan6 found that aluminum and zirconium improved thy low-temperature impact resistance of a low-alloy steel, while titanium was detrimental. Sims7 shows that sulphur increases the coarsening temperature and that the maximum coarsening temperature is between 0.04and 0.06 Per cent added aluminum. The

Jan 1, 1946

By E. H. Burdick

THE difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated mineral-spyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying 1 per cent is considered good grade; 0.7 to o.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of 1.0 per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent WO3 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 6o to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1942

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (&apos;) the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, (&apos;1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth&apos;s5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a &apos;-phase WO2, they reported the existence of two new phases. A 8&apos; phase, homogeneous between

Jan 1, 1949

By L. S. Darken

IT has long been recognized that the driving force in an isothermal diffusion process may be regarded as the negative gradient of the chemical potential (partial molal free energy) of the diffusing substance. This equivalence is exactly analogous to the fact that a mechanical force is the negative gradient of the potential energy. Nernst1 in 1888 expressed these driving forces in terms of osmotic pressure, which is directly related to the chemical potential and free energy. The relationship between the diffusivity, mobility and activity coefficient of electrolytes in aqueous solution has been developed in great detail by Onsager and Fuoss2 with results which have recently been confirmed experimentally by Harped and Nuttall.3 This interpretation of the driving force in isothermal diffusion has been discussed earlier by the author 4.6 who pointed out4 that "for a system of more than two components it is no longer necessarily true that a given element tends to diffuse toward a region of lower concentration even within a single phase region"; departure from the behavior of an ideal solution may be so great that the concentration gradient and the chemical potential gradient, or activity gradient, may be of different sign, thus giving rise to "up hill" diffusion. Since, in the discussion of that paper,4 some skepticism as to the validity of this conclusion was expressed, it seemed desirable to adduce experimental evidence to support it. Evidence of such diffusion in nonmetallic systems has already been reported. For example, it was observed by Hartley11 in a series of experiments in which sodium chloride diffused from a saturated solution in about 5 pct acetone in water into a solution virtually free of salt but with essentially the same acetone concentration. Specifically, a wine glass containing crystalline salt and saturated solution was totally immersed in a large glass cylinder containing the acetone-water solution without salt; the difference in specific gravity was such as to prevent convection. Diffusion of salt was accompanied by a marked depletion 0f acetone in the wine glass; after 3 days the acetone concentration decreased from 5.37 pct at the top of the glass, where the salt concentration was low (0.93 pct), to 1.84 pct at the bottom where the salt concentration was high (21.64 pct). This "uphill" diffusion was found to be such that the partial pressure (activity) of acetone was essentially equalized throughout the system when a steady state gradient of sodium chloride was maintained. In order to demonstrate the existence of such diffusion in metals, a series of four weld-diffusion experiments was made. In these measurements pairs of steel of virtually the same carbon content, but differing markedly in alloy content, were welded at the end and held at 1050°C for about two weeks. Subsequent analysis showed that carbon had diffused so as to produce an inequality

Jan 1, 1948

By A. Dubé, G. Letendre, C. E. Beaulieu

An experimental study has been made of the time dependence of internal .friction and modulus of rigidity in- freshly quenched steels at room temperature. The effects of frequency, composition, and various thermal treatments are given. The kinetic 1aws observed cannot be fully explained by the so-called first stage of tempering and the transformation of retained austenite. It is suggested that the observed phenomena are due to the progressive immobilization of dislocations introduced by the martensitic transformation. It is generally agreed that the conversion of tetraginal martensite into cubic ferrite and ce-mentite occurs in three stages which at moderate rates of heating take place in the following temperature ranges:&apos;-3 a) The first stage involves mainly a partial loss of tetragonality of martensite and the formation of ?-carbide between 95" and 175oC. b) The second stage consists of the decomposition of retained austenite between 230 and 290&apos; C. c) The third stage covers the formation of ce-mentite between 290o and 400&apos; C. The kinetic laws of these heterogeneous reactions have also been the subject of isothermal studies. Thus, Roberts, Averbach. and cohen3 report a very low reaction rate with a eutectoid steel at room temperature. For example, less than 10 pet of the contraction associated with the first stage is observed after 50 hr at room temperature. Hollonlon, Jaffe, and Buffum4 show that under the same conditions less than 10 pet of the tetragonality is lost. These results have led to the belief that martensite is a relatively stable phase at room temperature. On the other hand, it is well known that important structural changes occur in martensitic steels during the first few minutes at room temperature after quenching. This pretempering has at least two important consequences. In the first place, freshly quenched steels have a tendency to crack at room temperature, a fact which leads to the necessity of tempering as soon as possible after the quench. Another important consequence of pretempering a steel for short periods of time at room temperature is the stabilization of the retained austenite. Thus, as shown by Cohen,5 a very pronounced stabilization is effected with holding periods of 30 min at room temperature. Since these two effects are apparently not caused by the heterogeneous reactions mentioned above, they must be related to the rearrangement of structural defects within the martensite and retained austenite. According to the modern theory of dislocations, the shears required to effect the austenite-marten-site transformation may be realized through the motion of dislocations at the austenite-martensite interface and within the martensite plates.6 In this way, a martensitic transformation closely resembles a plastic deformation. In cold-worked solids, high concentrations of dislocations are left immediately after the plastic deformation and it seems reasonable to assume that appreciable densities of dislocations should also appear in the wake of a martensitic transformation. A considerable part of the high hardness of martensite would then originate in the obstruction of dislocations in analogy

Jan 1, 1961

By R. P. Fischer

A large production of vanadium during the war helped Germany to meet her critical requirements for the ferroalloy metals. Vanadium was needed not only in the ordinary high-speed too1 steels, but in other as a substitute for chromium, nickel, and molybdenum, which were scarce. Lacking a source of vanadium ore, however, the vanadium was obtained as a by-product of the steel industry—va-nadium-bearing pig iron smelted from iron ores containing about o. I per cellt V was blown in converters to yield vanadium-rich slag, from which vanadium was recovered by chemical treatment. The production capacity obtained was said to be about 6,500,000 lb. of vanadium a Year. Although the general Processes of Preparing vanadium-rich slags as well as the recovery methods described herein are known, some of the details presented may be of interest to both the American steel industry and the vanadium producers. No adequate data on the cost of the vanadium produced in Germany are known, but it seems likely that the cost exceeds the commonly quoted domestic price of about $1.10 per pound of contained VzOa. Information on the German vanadium production was obtained by a team of geologists from the Geological Survey* United States Department of the Interior, during investigations in May and June 1945 of the German utilization of low-grade raw materials. These investigations were sponsored by the Chief of Engineers, War Department. It is a pleasure to acknowledge the aid obtained from Messrs. H. C. Smith and J. D. Dickerson, investigators assigned to the Army Ordnance section of C.I.O.S., and Mr. C. F. Park, Jr., of the Geological Survey team. The data on vanadium recovery from iron ores were obtained from the Kaiser Wilhelm Institut fiir Eisenforschung, the Hermann Goring steel plant at Watenstedt, and from notes made by other investigators at other German steel plants. Preparation of Vanadium-rich Slags Most German iron ores contain only about 0.1 per cent vanadium, or even less, but some of the scandinavian iron ores available to the German iron industry in the past contain a little more than 0.1 per cent. In general German practice of vanadium recovery, nearly all of the vanadium in the ore goes into the pig iron, which is blown in the Thomas converter, yielding a slag containing about I per cent V. This slag is remelted, the vanadium again going with the iron, which is again blown in a converter, yielding a slag that averages about 10 per cent V. This slag is treated at special chemical plants, by the process of a sodadizing roast, water leach, and acid precipitation of vanadium oxide. The Herman Goring steel plant at Watenstedt used the low-grade Salzgitter iron ores, the average composition of which is shown in Table I, column I. The acid and basic iron produced in the blast furnaces contained about 0.3 per cent V. A Thomas

Jan 1, 1948