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By Zay Jeffries

THE object of the present paper is to enlarge somewhat on the general principles advanced in my discussion 1 of Mathewson and Phillips' article on. The Recrystallization of Cold-Worked Alpha Brass on Annealing.2 It will also serve as an acknowledgment of Prof. Howe's3 most important remarks on my contribution. In this paper the writer has adopted Prof. Howe's suggestion to substitute the term "germinative temperature" for "critical temperature for grain growth." Instead of being an exact or certain temperature it should be considered that the germinative temperature phenomenon exists throughout a small temperature range. Factors Influencing Fast Growth Phenomena The development of grains of macroscopic size at the germinative temperature should be considered the extreme condition of a general rule. When considered in this light it is not strange that the development of these large grains should be the exception and not the rule. The principal factors influencing the operation of the laws of fast growth temperature are as follows: 1. Rate of heating.

Jan 10, 1916

By Francis T. Havard

A Reply to the Discussion by Mr. Francis T. Havard of the Paper by Mr. Henry W. Edwards, which was read at the Atlantic City Meeting, February, 1.904. (Annual Meeting, February, 1905.) MR. HENRY W. EDWARDS, Grand Junction, Colo. (communication to the Secretary) :* Effect of Heat. It should be remembered that the coefficient of expansion of concrete is nearly that of iron; therefore in constructing flues the design must take account of this important detail. The cracking of flues, mentioned by Mr. Havard as having occurred at a temperature of 100° C. and above, . were possibly caused by neglecting to appreciate the extent of the expansion and contraction of the concrete. Effect of Atmospheric Moisture.-The moisture present in the atmosphere is exceedingly injurious to flues of any material, and those made of concrete are no more susceptible than of brick. My experience with flues of the Monier construction, having walls from 1.5 to 2.5 in. thick plastered upon a net-work of iron rods, was unsatisfactory from the standpoint of dura¬bility.

Mar 1, 1905

By H. A. Wriedt

At 500°C (932°F) the range of y' iron nitride is from 5. 77 + 0.03 wt pct N (in coexistence with a iron) to 5.88 * 0.03 wt pct N (in coexistence with E iron nitride). Stoichiometric "Fe,N" (5.900 wt pct N) is near the upper extreme of possible compositiom. The depe-dence of nitrogen activity (expressed as pnh,/Ph,) on nitrogen content is described satisfactorily by a "Langmuir" isotherm: At even the highest nitrogen concentrations, less than 0.18 pct of' the nitrogen atoms present are impositions of disorder. Past investigations1-4 of the Fe-N system have left only details of the thermodynamic behavior of the y' nitride, "Fe,N9', to be studied. The present investigation was made to establish more precisely than hitherto the limits of composition and the relation between composition and nitrogen activity at 500°C. EXPERIMENTAL TECHNIQUE The compositions of nitrides in equilibrium with various NH, + Hz mixtures at 500°C were determined from the weights gained by 0.02-in.-thick (4.0 to 4.5 g) strips of purified iron* when the nitrides were formed A description of the gas generation and furnace system has been published.5 Cracking and blistering during conversion of the original solid iron at 550°C injected considerable porosity into the strips without causing their disintegration. The time for complete conversion was significantly lowered by periodically reducing partly nitrided specimens in hydrogen and then reexposing them to the nitriding gas. Gas mixtures producing single-phase were used in the equilibrations at 500°C. Equilibrium was regarded as existing when the specimen weight was not detect-ably affected by further exposure to the same conditions. The gas compositions and nitrogen activities at which y' transformed to a iron (lower activity limit) and to E iron nitride (upper activity limit) were redetermined during the investigation. A specimen was equilibrated in an NH, + Hz mixture at 500°C and then exposed to a s1ightly different gas. When equi- librium had been reestablished the gas was again changed slightly. At each stage of this repeated process, while the specimen was reacting with the gas, the variation of its weight with time was observed. The onset of phase transition was marked by an abrupt change in the amount and rate of weight gain or loss. The specimens were weighed outside the furnace, in air and at room temperature, on a balance with 0.05 mg precision. When it was found that the specimens were oxidizing at a significant rate during the weighing, a series of timed weighings was made with each specimen, starting 1 min after its exposure to air. RESULTS AND ANALYSIS The gain in specimen weight from oxidation during weighing was linear in the logarithm of time between 1 min and about 2 hr, Fig. 1, later becoming linear in the cube root of time. In the logarithmic period, nitride specimens oxidized two to three times as fast as

Jan 1, 1970

By S. H. Cathcart

Price, production and drilling operations exceeded any year since 1930. A top price for crude of $2.55 was maintained from May 1 to November 6 and increased activity about coincides with that period. The average crude price for the year was: Bradford, $2.46; Kane-Butler, $2.34; Southwest Pennsylvania, $2.13. Production for the year exceeded 15 million barrels, an increase of about 2 million barrels over 1933. That this increase was more than justified by market demand is indicated by a reduction of 892,000 bbl. in stocks for the year. Two classes of data appear on Table 1, which are differentiated by footnote references. Where possible the .figures were obtained from individuals and companies that, from long acquaintance and varied contacts, are most capable of supplying an estimate where an estimate is necessary. The remaining data represent a rather careful compilation from all available published records (see p. 378). Drilling operations and production as summarized by the Oil City Derrick are as shown on Table 2.

Jan 1, 1935

By David Cole

The appearance of the Wilfley table in 1897 marked an epoch in the art of concentration of ores. The table has merited and received an almost unprecedented measure of public approval, lasting through its whole patent life. It has been very little improved in itself, or improved upon by competitors. The new machines bidding for popular favor have been of the Wilfley family, but without ability to do markedly better work than the parent machine, or to do more work except by the use of superimposed decks, the latter having obvious disadvantages. During the past three years there has been developed at Morenci a new type or arrangement of riffles applicable to the Wilfley type of concentrating table which corrects many of the objectionable features or limitations of the older system and obviates most of the difficulties encountered with it, particularly when handling ores having a low ratio of concentration. The new type is known as the Butchart1 riffle system, and its general arrangement is shown in Figs. 1 and 2. The old system accomplished stratification satisfactorily but has

Jan 1, 1915

By Karl Cohen

The question of attainment of competitive nuclear electric power is of interest to uranium producers because the rate of attainment of this goal determines the date when there will be a solid, non-political, domestic uranium market. It is a burning question to those of us in the civilian nuclear power business, because our entire business future hinges on how well, and how soon, we can make electricity from nuclear reactions at prices comparable to electricity from coal. For an idea of the magnitudes involved, consider that the first fuel load of the Dresden (Illinois) nuclear power station, plus spares, will be about 90 tons of 1.5 pct UO2. This requires about two-and- a-half times as much natural uranium oxide feed to the diffusion plant, or 225 tons. This, in turn, represents about a month's production from the nearby Uranium Reduction Co. mill. Note also that the 180,000 kw electric output of the Dresden station will be about 0.1 pct of the national electric generating capacity in 1960.

Jan 12, 1958

By Rupert Spivey

Kennecott Copper's Chino mine is one of the oldest copper mines in the United States, having been operated by the Spaniards as early as 1800. At that time haulage methods were indeed primitive. Indians brought the ore up on "chicken ladders" in leather buckets. It was then melted into crude bars and hauled to Chihuahua by mule train. There are still remnants of the old trails near the present pit where the mule hooves cut grooves in solid rock. The mines were worked as underground operations off' and on until open-pit mining was started in 1910 by John Sully and Daniel C. Jackling. Since that time many haulage methods have been used: mule carts, steam and electric trains and finally large haulage trucks, now believed to be the best method for this mine. The general shape of the pit is oval with dimensions of 1% miles by 1% miles. Working benches are 50 ft high, with the bottom bench at 5750 ft and the top at 6450 ft above sea level.

Jan 1, 1964

By R. G. Carlson, F. E. Westermann

HOT pressing of powder particles has gained importance recently, since it affords a method in which high densities are rapidly attained. In a recent study on hot pressing of alumina powders, Mangsen, Lam-bertson, and Best1 have shown within the limits of their experiment, the validity the rate equation for densification in hot pressing, originally proposed by Murray, Livey, and Williams.2 i.e., where D = fraction of theoretical density, t = time, P = pressure and 77 is the viscosity, all in appropriate units. This equation was derived from earlier work of Shuttleworth and Mackenzie3 which is based on the closing of spherical pores under the action of surface tension. The integrated form of this equation yields a straight-line relation between log (1 - D) and t. Such conditions were found by Felten4 to be true only after extended periods of pressing. In an endeavor to quantitatively evaluate the exactitude of this equation in the initial sintering stage, i.e., prior to sealing of the pores, spherical anti-

Jan 1, 1962

By T. D. Yensen, N. A. Ziegler

The elements aluminum,' arsenic,2 silicon,3 tin2 and vanadium,~.~ when used in relatively small amounts as alloying elements, seem to have a beneficial effect on the magnetic properties of iron—i. e., they increase the maximum permeability and decrease the coercive force—whereas there are definite indications that boron,5 carbon,6 nitrogen: oxygen," phosphorus16 sulfur6 and titaninum,~ as well as the metals of and adjacent to the ferromagnetic group, nickel,~ cobalt,1° copper," and manganese,% have a detrimental effect on these properties. The effects of calcium4 and magnesium4 are small, if any, while the effect of chromium12 in small amounts is unknown and in large amounts is generally detrimental. WeveR's Classification13 All chemical elements may be divided into three classes based on their effect on the allotropic transformation points of iron. Class 1 contains the nonmetallic elements (except phosphorus) and these lower the A3 point and raise the A4 point. Class 2 contains the common metals and

Jan 1, 1931

By V. C. Allen

THE Tri-State Zinc, Inc., Galena, Ill., was confronted with the problem of securing ore from a deposit because the hoisting shaft was several thousand feet from the mill. The orebody is several thousand feet long, averaging 200 ft in width and 60 ft in height and opened up by vertical shafts some 300 ft deep. Mining is by the room-and-pillar method. During the initial operation the ore was loaded by conventional electric 1/2 -yd boom-and-dipper shovels and hauled to the shaft by 8-ton diesel trucks. This underground ore loading and hauling was well adapted to the conditions and productive of low costs per ton. However, with the mill situated as mentioned, a triple handling of all broken rock was necessary: 1-from the stope to the shaft by truck, 2-up the shaft by skip or can into the surface hopper, and 3-by truck from the surface hopper to the crushing plant at the mill. In addition to the repeated handling, serious troubles were encountered during the winter because of freezing in the shaft hopper.

Jan 6, 1951

By E. I. Salkovitz, F. W. von Batchelder

AS Slawson1 and others have already shown, from a geometrical view twinning in the diamond structure may be considered as a reflection across a (111) plane or as a reflection across a (112) plane. An analysis by Ellis and Treuting2 showed that the twinning plane must be the (111) plane, but that a twin might have lateral boundaries along (112) planes. Earlier Slawson1 and Ellis3 had shown that only (111) twinning was present in diamond and germanium respectively. Since an ingot of silicon, 1 in. in diam and 1 1/2 in. long, prepared from Dupont silicon to which 0.2 pct Be had been added was available, it was examined for twinning. The ingot had been cooled slowly from the bottom. A section 1/16 in. thick was ground off from the bottom and then the ingot was sliced vertically through the center. Spectrographic analysis indicated only faint traces of iron and silver, in addition to the beryllium. The sample was first etched with a hot solution of 10 pct NaOH in water.and photographed. Back-reflection Laue patterns were made of the vertical and horizontal sections in the regions designated in Fig. 1. Orientations were obtained for each twin using the Greninger technique. Several regions of the same orientation were found; thus regions A and K were identical, similarly N and P, and C, G, J, and L. Knowing the angles between the traces of the twinning plane on the surface and the specimen axis, the indices of the twinning plane were deduced. In all cases the twinning plane was found to be (111); lateral boundaries, however, were found which were (112) such as the one indicated in Fig. 1. Therefore, as in the case of diamond1 and germanium' only (111) twinning occurs in silicon. We wish to thank Mr. Hino for the use of the ingot as well as for its metallographic preparation. References 1C. B. Slawson: American Mineralogist (1950) 35, p. 193. 2 W. C. Ellis and R. C. Treuting: Trans. AIME (1951) 191, p. 53; Journal of Metals (January 1951). 3W. C. Ellis: Trans. AIME (1950) 188, p. 886; Journal of Metals (June 1950).

Jan 1, 1953

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique's possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958

By Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964

By Klaus Detert, Joseph Ziebs

The progress of primary recrystallization has been studied in alloys of nickel with 0.01, 0.1, and 1.0 at. pct Ta. It can be shown that in one particular alloy containing 0.1 Ta and 0.02 02 a large grain structure (0.5 mm diameter) could he developed by primary recrystallization in thin sheetswhich were cold-worked to 97.5 pct reduction in thickness. Electron transmission microscopy demmstrates that this phenonmena was linked to the occurrence of fine precipitates at subboundaries. A discussion of how fine precipitates can exert under certain circumstances a rather distinct retarding effect on nucleation rate is included. IN a former investigation, the recrystallization and texture formation in a series of binary nickel alloys including pure nickel were studied.&apos; Nickel alloys with some tantalum added displayed peculiarities during primary recrystallization which have been studied in more detail by the present investigation. The alloys were prepared by powder-metallurgy techniques similar to the previous investigations.&apos; Pure metal powders were thoroughly mixed to obtain alloys with 0.01, 0.1, and 1.0 at. pct Ta, referred to as alloy A, B, or C, respectively. The metallic impurities were kept below 0.005 at. pct except iron and cobalt with slightly higher values, by using highly purified nickel and tantalum powders.&apos; The mixtures were pressed into bars and sintered at a temperature of 1300°C. The sintering atmosphere was either high vacuum, dry hydrogen, or wet hydrogen. The sintered rectangular bars were rolled 60 pct to a thickness of 3 mm, then annealed under dry hydrogen at 1000°C and again cold-rolled to about 97.5 pct reduction of thickness. After this heavy deformation, the sheet thickness was 0.07 5 mm. In order to study primary recrystallization which occurred in measurable times between 400" and 600°C, samples of the rolled sheets were annealed in a salt bath at various temperatures for various times in order to study the progress of recrystallization by hardness measurements and microscopic examination. For optical observation, the samples were polished and etched in a solution of 65 cu cm HNO3, and 18 cu cm acetic acid in 20 to 100 cu cm H2O, depending of the particular sample and annealing treatment. For transmission electron microscopic observations, thin foils were prepared by the combined window and Bollmann techniques.273 The electrolyte consisted of 23 pct perchloric acid and 77 pct acetic acid held at 15°C. Polishing was performed at a current density of 0.4 amp per sq cm. The examination of the thin films was accomplished by a Siemens Elmiscope-type electron microscope operating with an accelerating voltage of 100 kv. RESULTS The progress of primary recrystallization was very accurately followed in these alloys in order to establish the time when recrystallization started and ended during an isothermal anneal. Table I gives some of the data obtained by these studies. The time for beginning is a mean value, where somewhat less than 5 pct of the matrix has recrys-tallized. The end of recrystallization is the time when at least 95 pct of the matrix has recrystal-lized. Listed are three different B alloys, with 0.1 Ta distinguished by different sintering atmospheres which influence the rate of primary recrystallization. By the above method, the state of the grain structure when primary recrystallization was completed, but grain coarsening had not started, could be clearly defined. The average grain diameter of the recrystallized matrix is also given in Table I. The grain size did not depend on the temperature of the isothermal anneal. With one exception the grain size of the primary recrystallized matrix was found to be rather fine

Jan 1, 1965

By P. S. Kotval, H. Hahell

PRECIPITATION of M23C6 carbides at grain boundaries in austenitic steels and nickel base superalloys has received considerable attention. Hatwell and Berghezan,1 in a study using carbon extraction replicas, observed that dendritic growth of the M23C6 carbide phase occurred at grain boundaries in austenitic steels. Merrick and Nicholson2 have observed that in thin foils of "Nimonic 75" alloy the precipitation of M23C6 carbide was discontinuous at grain boundaries. Lewis and Hattersley3 have suggested that the type of M23C6 precipitation observed in Ni-Cr austenites represented the early stages of discontinuous precipitation. In a more recent study, Singhal and Martin4 have concluded that grain boundary M23C6 precipitation involves the migration of an austenite grain boundary by a mechanism very similar to that proposed by Tu and Turnbull.5 Tu and Turnbull&apos;s suggestion essentially involves grain boundary migration under the driving force arising from the difference between the surface free energies of the opposite sides of the plate. Thus, Singhal and Martin&apos;s observation4 implies that the first stage of discontinuous precipitation has taken place and that the grain boundary has provided a diffusion short circuit for the sub-stitutional solute atoms (principally chromium) which assist the preferential growth of the M23C6 plate in contact with the grain boundary. However, no evidence of the characteristic cellular morphology typical of discontinuous precipitation was found in Singhal and Martin&apos;s studies. Presumably, this is due to the low volume fraction (i.e., low supersaturation of solute) of the precipitating carbide reported by Singhal and Martin.4 Recently, Raymond6 has studied precipitation of the M23C6 carbide in Incoloy alloy 825 and shown that the growth of this phase is perpendicular to grain boundaries at 1400°F and in the plane of the grain boundary at 1700°F. The former aging condition resulting in discontinuous or "cellular" precipitation. Raymond has suggested an explanation for this behavior based on the relative rates of chromium diffusion by volume and grain boundary diffusion at the two different aging temperatures. In the course of a recent investigation on precipitation behavior in several &apos; strengthened superalloys, precipitation of M23C6 carbide at grain boundaries was studied. Under conditions of a high degree of supersaturation, the M23C6 carbide precipitates in the discontinuous or cellular morphology in Waspalloy (Ni-18.51 Cr-2.0 Fe-3.53 Mo-1.16 Al-2.78 Ti-0.09 C). This note presents electron microscopy observations of this mode of precipitation and its effect on mechanical properties. Specimens of Waspalloy after "solution" heat treatment at 1950°F show essentially single phase matrix with a few residual particles of "primary" MC carbide. In normal commercial heat treatments, precipitation of Ni3(Al,Ti) ordered fcc r&apos; phase occurs throughout the matrix and M23C6 precipitates as globular particles at the grain boundaries. In these commercial heat treatments the degree of supersaturation during precipitation is low. However, if specimens of Waspalloy are quenched from the solution heat treatment temperature of 1950°F and then aged at an aging temperature where the degree of supersaturation is high, discontinuous precipitation of M23C6 occurs. Figs. 1 and 2 show thin foil micrographs of Waspalloy, solution heat treated at 1950°F, water quenched, and aged at 1292° and 1598°F, respectively, for 500 Fig. 1—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 500 hr at 1292°F. Magnification 15,500 times. Fig. 2—Thin foil of Waspalloy, solution heat treated at 1950°F for 1 hr, water quenched, and aged for 114 hr at 1598° F. Magnification 13,000 times.

Jan 1, 1970

By Eugene F. Broome, Hugh A. Walls

Self-diffusion coefficients were measured using the modified shear cell technique over a temperature range from 31" to 401°C. These data agree within experimental error with those of Petit and Nachtrieb, which were determined from 30°to 99°C. LIQUID self-diffusion behavior in gallium has been studied previously by Petit and Nachtrieb&apos; using their shear cell technique.&apos; Data were obtained in that investigation over temperatures ranging from 30.6 to 98.7"C, and these comprise the only published data for liquid gallium. In the work reported here, diffusion data were obtained from 30.8 to 400-9.Cusing a shear cell technique different from that of Petit and Nachtrieb. This modified shear cell method and the mathematical analysis for diffusion in a finite capillary geometry have been previously described.3 PROCEDURES AND ANALYSIS The segments of the modified shear cell were fabricated from types 304 and 316 stainless steel. No corrosion problems with gallium were encountered until attempts were made to obtain data at 500°C. The diffusion capillary diameter was 1.59 mm and capillary lengths for the four sets of cell segments used are given in Table I. Gallium with a purity of 99.999 wt pct was obtained from Var-Lac-Oid Chemical Co. The gallium-72 isotope used to measure the self-diffusion coefficients was produced from this inert gallium by irradiation in The University of Texas Reactor Facility, and was checked for radiochemical purity. Following a period of isothermal diffusion controlled to within 0.0l°C, the contents of each capillary section were emptied into a counting planchet, weighed to assure that gallium had not been lost during handling, and the radioactivity determined by windowless gas-flow proportional counting. Great care was taken to obtain a reproducible counting geometry for the samples. Diffusion coefficients were obtained from the solu-tion3 to the diffusion equation for the modified shear cell problem, viz.: in which B2= C2(t)Li + L2)- CSL1-COL2 P* (C0-Cs)(L1+ L2) and L, and L2 are the capillary segment lengths. The step-function initial concentration distribution was expressed as C(x,O) = C, for -L1 = x < 0 and C(x,O) = Co for 0 < x 5 L?. Also, C2(0 = ^- fcix,t)dx Computation of the diffusion coefficients was done numerically as described in our earlier paper.3 Because of the short half-life of gallium-72 (14.1 hr) and the relatively long counting times taken to give a precise value of the diffusion coefficient, it was necessary to account for the radioactive decay both during the actual count and between counts for different samples (before and after diffusion). Thus, the average count rate Cz(t) for a second sample counted from times t3 to t4 can be made consistent with the average rate Co determined for a first sample counted from times t1 to t2 by the relationship: N(e-»i-e-M») , , C2(f) " &-«,)(*-«.-«-»«) [21 in which N is the total number of counts taken and is the decay constant. RESULTS AND DISCUSSION The self-diffusion coefficients determined in this investigation are listed in Table 11. Values of the parameters used to calculate the coefficients are given in the table, as are values of the random counting error &apos; for the concentration ratio pz and the corresponding expected random variation AD in the diffusion coefficient. The quantity is calculable from: &apos;Cg — C2(t)} , „ ,2 .-„¦, M co-csl(ACs)J W in which AC is the error in the individual count rate. The mean values of the diffusion coefficients within each temperature group are also given in Table 11. Such temperature groupings of data are reasonable because of the small variations between the temperature~.~

Jan 1, 1970

By D. B. Robinson, J. Lukacs

A knowledge of the equilibrium water content of hydrocarbon systems under pressure is important to the natural gas industry. The information available on the solubility of water in hydrocarbon, hydrogen sulfide, and carbon dioxide systems is reviewed in this paper and the influence of the more important variables such as temperature, pressure and molecular structure on solubility in liquids and gases is discussed. A suitable cbromatographic technique has been developed for determining low concentrations of water. Tailing of the water peaks has been elim inated by adding water to the carrier gas stream The method is applicable for both gas or liquid samples and is effective in the presence of hydrogen sulfide. The experimental study of water solubility in methane-hydrogen sulfide systems at a temperature of 16oF has shown that the presence of hydrogen sulfide causes only a modest increase in water content at pressures up to 1,400 psia. Theoretical considerations and data on pure hydrogen sulfide and carbon dioxide suggest that the effect of both these compounds will be greater at higher pressures and in the liquid phase. INTRODUCTION Before transporting or processing natural gases and gas condensates, it is usually necessary to dry them using suitable dehydration equipment. The design and operation of this equipment requires a knowledge of the amount of water present in the fluid at the reservoir and operating conditions. This is influenced by temperature, pressure and composition, particular1y when certain non-hydrocarbon components are present. Field experience indicates that hydrogen sulfide and carbon dioxide, for example, alter the usual water solubility relationships appreciably. However, an extensive search of the literature does not reveal any quantitative data on such systems. For sweet natural gases, generalized empirical correlations such as the one proposed by Katz, et al,6 can be used to predict water solubility with confidence at most temperatures and pressures of interest. However, existing theoretical relationships do not permit a calculation of the deviation from these curves when polar substances like hydrogen sulfide are present in the system. Thus one must resort to an experimental approach to obtain the necessary information. The fact that laboratory experimental methods frequently involve the use of mercury which reacts with hydrogen sulfide in the presence of water, and that hydrogen sulfide interferes with many chemical reactions specific for water has contributed to the difficulty of studying water solubility in systems containing hydrogen sulfide. In this investigation the water content of a limited member of methane-hydrogen sulfide mixtures was determined using a special technique with gas chromatography. REVIEW OF PUBLISHED DATA Experimentally determined water solubility data have been reported for methane, 14 ethane, 15 propane, 9 n-butane, 16 1-butene, 11 hydrogen sulfide 18 and carbon dioxide. 19 These studies report the effect of pressure, temperature and molecular structure on water solubility in single component gases and liquids. Fig. 1 compares experimentally determined water solubilities in several hydrocarbons, carbon dioxide and hydrogen sulfide at l00F as taken from this

By N. S. Stoloff, R. G. Davis

It is concluded from an X-ray stztdy that the formation of the hcp Mg3Cd superlattice is a nuclea-tion and growth reaction. A two-phase, ordered-plus-disordered, region is observed between 153" nnd 141"C. A maximum in the flow stress is observed both at temperature and in quenched specimens within the two-phase region. The peak arises fro112 the extra energy required to create antiphase boundary upon cutting the ordered regions. Hardening during isothermal annealing in Mg3Cd has been shown to be similar to the domain hardening in Cu3Au-type alloys in that up to the maximum the structure is ordered domains growing into a short range ordered matrix. The hardening is due to a combination of short range order strengthening and the strengthening produced when antiphase boundary has to be created. In a recent study1 of the effect of long-range order upon the mechanical properties and deformation modes of hcp Mg3Cd a comparison was made be- tween quenched (disordered) and slow-cooled (fully ordered) specimens. The most striking observations were that the disordered alloy yields at a much higher stress than the ordered alloy, and that there is a change in slip mode from primarily (_0001) ba_sal slip in the disordered state to (0001), {1010}, {1122}, and {l011} slip in the ordered state. The main purpose of the present work is to extend these observations to determine whether MgsCd exhibits a peak in flow stress at an intermediate degree of order, or at a critical domain size, as do other orderedstems. However, disagreement exists about the Mg3Cd order transformation with respect to: 1) the location of the critical temperature for order, 165°C or 153"~,&apos; and 2) how the degree of order varies with temperature. Welber et a1.5 concluded from specific heat measurements that the formation of Mg3Cd is a second-order reaction with the degree of order a continuous function of temperature, while Moore and Raynor concluded that it is neither a first-order reaction, with the degree of order a discontinuous function of temperature, nor a second-order reaction. Consequently it was considered necessary to undertake an X-ray investigation into the change in degree of order and structure in the

Jan 1, 1964

By F. B. Foley

With the possible exception of high-speed tool steel, the service demanded of rock-drill steel is probably more precarious than that of any other tool steel. Unaided by the helpful influence of alloys and dependent solely on the efficiency of the heat treatment applied for its ability to stand up under the abuse to which it is necessarily subjected, rock-drill steel is worthy of intensive study. For its heat treatment the smith has his fire, an oil fire perhaps, and a quenching bath; he judges the temperature by his eye. There are shops where excellent drills are produced by this method, but there are more where the product varies between very good and very bad. Pyrometers with specially designed equipment are used in but few cases. But the responsibility for rock-drill failures does not rest entirely on the smith. Little has been published concerning the efficiency of drill steel, though the Canadian Mining Journal1 published the breakage record of a large number of hollow drill steels. This record indicates that most of the breaks occur during the early life of the steel and that as a given batch of steel is used, its percentage of breakage decreases. This fact, the article points out, is at variance with the much-talked-of theory concerning failure from crystallization and fatigue. It seems to point to the fact that the greater part of drill-steel failure from breakage is traceable to faulty manufacture, resulting in defects in the bore of the hollow steel from inclusions of slag or oxides, etc. As this defective material meets with early failure, it is weeded out. In addition, some breakage may be caused by a lack of proper condition with respect to heat treatment of the steel as furnished by the manufacturer. In the article mentioned, the breakage of 1/14-in (3.17 cm.) hollow steel is given as 4.62 per cent. for the early period of use, with a decrease to 3.35 per cent. and 2.67 per cent. with time in use. For 1-in. (2.5 cm.) hexagonal hollow steel, the figures for breakage are 0.18 per cent. and 0.06 per cent.; attention is called to the great decrease in breakage by the use of smaller diameter drills. The figures are given as so many drills sharpened, but there is no way of determining the percentage of

Jan 1, 1922

By T. C. Desollar

The group of iron-ore mines known as the Red Ore Mines, owned and operated by the Woodward Iron Co., is on Red Mountain approximately ten miles southwest of Birmingham, Ala. At the present time NO. 1 and No. 3 mines are active, No. 2 mines having been abandoned in 1928. Ore from this group of mines was first mined in 1882, and originally came from open cuts along the outcrop, but, when the "soft ore" (weathered hematite) was mined out and the harder ore was encountered, it became necessary to develop the orebody by means of slopes driven in the ore formation. The three mines to date have produced more than 22,000,000 tons, and the two operating mines now have a capacity of over 1,000,000 tons per year. Geology The U. S. Geological Survey has described the features of the district. It places the hematite of Red Mountain, commonly called "red ore," in the Clinton formation of the Silurian system. This formation varies from 200 to 300 ft. in thickness, and is composed largely of shale (slate) and sandstone. There are four iron orebeds in the formation, known as the Hickory Nut, Ida, Big Seam and the Irondale seams. The strike of the orebeds is northeast and southwest, and the dip is southeast, the outcrops being on the west side of the mountain. The two seams that have been worked at the Red Ore mines are the Big Seam and the Ida. The Big Seam, which is and has been the principal source of the ore mined, is approximately 20 ft. thick and consists of hematite and ferruginous bands of sandstone. It is separated into "upper" and "lower bench" ore by a slate parting that is about 30 in. thick. All present mining is confined to the "upper bench" ore, which is uniform in texture and drills and breaks fairly easily when the holes are placed so as to take full advantage of the face of the ore. Typical analyses are shown in Table 1. The presence of two water-bearing formations, the Fort Payne chert and the Hartselle sandstone, lying respectively 160 and 300 ft. above the Big Seam, make it essential that in mining the ore any movement of

Jan 1, 1934