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By Donald E. Grimes

In conjunction with Inland Steel&apos;s development of lead-bearing steels possessing improved machin-ability because of tellurium and/or selenium additions, it was decided to determine liquidus and solidus temperatures in the Pb-PbTe-PbSe sub-ternary system. With the exception of alloys in the PbTe-PbSe system, it is believed that no previous study of this subternary has been performed. Thermal analysis was employed in a general survey of the subternary. In addition to PbTe, PbSe, and pure lead, ten ternary compositions were selected at intervals of ten at. pct. Sixty-gram alloys were prepared by sealing an appropriate mixture of the elements in quartz crucibles with a central thermocouple-well under a vacuum of less than 10 p. All three elements were 99.999+ pct pure with only trace impurities detected by spectroscopic examination. After the alloys had been heated at least 20°C above the liquidus in a Kanthal furnace, cooling and heating curves were obtained. Two or more cooling curves were employed both for the determination of each alloy liquidus and for the solidus of those al- loys containing greater than 50 at. pct Pb. Cooling rates were 0.5° to 3.5°C per min during the 5 min immediately prior to the start or end of solidification. For those ternary alloys containing 50 at. pct Pb, the solidus was determined from heating curves. Temperatures were measured with a Pt/Pt-10 pct Rh thermocouple which was calibrated in the same apparatus against the freezing points of zinc (A. D. MacKay—99.999 pct), antimony (A. D. MacKay-99.999 pct), and copper (ASARCO—99.999+ pct) both before and after the experimentation. The only interruptions in the continuous strip-chart recording of the temperature occurred for brief periods at significant points of interest when direct readings were made with a Rubicon Type B potentiometer sensitive to * 1 µv. The average liquidus and solidus temperatures obtained in this investigation are listed in Table I together with probable errors based on the accuracy of the thermocouple calibration and the reproduci-bility of the data. No chemical analyses of the alloys were performed because the synthetic or as-charged compositions were felt to be reliable. The melting points obtained for PbTe (924.7° ± 0.7°C) and PbSe (1084.0° ± 0.6°C) compare favorably with recent findings of other investigators.&apos;-&apos; As indicated in Table I, both the liquidus and solidus temperatures increase as selenium replaces tellurium for a constant atomic percent lead. As a result, the ternary liquidus and solidus temperatures for a given percent lead lie between the corresponding binary temperatures published in the literature. It should be noted that those ternary alloys containing 50 at. pct Pb exhibit a relatively narrow liquid-plus-solid region (<80°C) when compared with alloys containing greater than 50 at. pct Pb. Alloys with 60, 70, or 80 at. pct Pb not only have a much wider liquid-plus-solid region (>500°C) but also exhibit considerably lower and approximately constant solidus temperatures which thus form a virtually isothermal solidus "plane" slightly below the melting point of pure lead (327.3°C). For these alloys

Jan 1, 1965

By P. P. Gregory

The rate of drilling operations in the West Texas district during 1940 was approximately equal to that of 1939. The total number of wells dillled in the area during the year was 1834, of which 1716 were completed as oil producers, 12 were gas wells and 106 were dry holes. The number of wildcat wells drilled during the year was comparatively small. The drilling of inside locations in proven areas and the drilling of wells for the purpose of extending the productive limits in producing fields constituted the bulk of development during 1940. Gaines County led all other counties in the district in the total number of oil-well completions. The oil production totaled 83,345,381 bbl., the highest figure for any year since proration was begun. The 1940 oil production exceeded the 1939 production by approximately four million barrels. Discoveries While comparatively few new oil-producing areas were discovered during 1940, it appears that the oil production found in simpson lime in the Abell field, pecos County, was an outstanding discovery for the year. This was the second Ordovician discovery in Pecos County. Taubert, McKee & Siemoneit located its discovery well, V. W. Crockett No. 1, set. 4 1/2 H. & T. C. R.R, co, survey in the Imperial area of northwestern Pecos County. The top of pay was encountered at 5270 ft., and the well was bottomed at 5357 ft. in simpson lime, on act. 17, I940. The initial production was 928 bbl. of 43" gravity sweet oil in 11 hr. 23 min., flowing naturally through 2-in. tubing with gas-oil ratio of 783 cu. ft. per barrel. Following the completion of the discovery well, large blocks of land were leased in the area, and several locations were made toward the close of the year. There is every indication that the Abell field will become a major producing field in the West Texas district. There was no pipe-line outlet for the field at the end of the year. Shipley-Silurian field, discovered by the Gulf Oil Corporation, appears to be another major addition to the oil reserves in 1940. The discovery well, Wristen Brothers No. 5, is in sec. 18, block 5, H. & T. C. R.R. Co. survey in Ward County. The well was drilled to a total depth of 9187 ft. and was plugged back to 7075 ft. The Silurian lime section was acidized with 3000 gal., from 6993 to 7075 ft., and on Dec. 5, 1940, the well was completed for initial production of 3040 bbl- of 32.2" gravity oil in 24 hr., flowing through tubing. Todd Deep field, Crockett County, was discovered by the Continental Oil Co. et al. The discovery well, J. S. Todd No. 2, set. 29, block WX1 G.C. & S.F. R.R. Co. survey, was completed on April 3, 1940. The top of pay was encountered at 5623 ft., and the well was bottomed at 5691 ft. for initial production of 1613 bbl. of 40.6&apos; gravity oil flowing naturally through 2-in. tubing. The pay section was found in Strawn lime of Pennsylvanian age. There were six producing wells in the field at the end of the year. This appears to be another major discovery in 1940. There was no pipe-line outlet in the field at the end of the

Jan 1, 1941

By P. P. Gregory

The rate of drilling operations in the West Texas district during 1940 was approximately equal to that of 1939. The total number of wells dillled in the area during the year was 1834, of which 1716 were completed as oil producers, 12 were gas wells and 106 were dry holes. The number of wildcat wells drilled during the year was comparatively small. The drilling of inside locations in proven areas and the drilling of wells for the purpose of extending the productive limits in producing fields constituted the bulk of development during 1940. Gaines County led all other counties in the district in the total number of oil-well completions. The oil production totaled 83,345,381 bbl., the highest figure for any year since proration was begun. The 1940 oil production exceeded the 1939 production by approximately four million barrels. Discoveries While comparatively few new oil-producing areas were discovered during 1940, it appears that the oil production found in simpson lime in the Abell field, pecos County, was an outstanding discovery for the year. This was the second Ordovician discovery in Pecos County. Taubert, McKee & Siemoneit located its discovery well, V. W. Crockett No. 1, set. 4 1/2 H. & T. C. R.R, co, survey in the Imperial area of northwestern Pecos County. The top of pay was encountered at 5270 ft., and the well was bottomed at 5357 ft. in simpson lime, on act. 17, I940. The initial production was 928 bbl. of 43" gravity sweet oil in 11 hr. 23 min., flowing naturally through 2-in. tubing with gas-oil ratio of 783 cu. ft. per barrel. Following the completion of the discovery well, large blocks of land were leased in the area, and several locations were made toward the close of the year. There is every indication that the Abell field will become a major producing field in the West Texas district. There was no pipe-line outlet for the field at the end of the year. Shipley-Silurian field, discovered by the Gulf Oil Corporation, appears to be another major addition to the oil reserves in 1940. The discovery well, Wristen Brothers No. 5, is in sec. 18, block 5, H. & T. C. R.R. Co. survey in Ward County. The well was drilled to a total depth of 9187 ft. and was plugged back to 7075 ft. The Silurian lime section was acidized with 3000 gal., from 6993 to 7075 ft., and on Dec. 5, 1940, the well was completed for initial production of 3040 bbl- of 32.2" gravity oil in 24 hr., flowing through tubing. Todd Deep field, Crockett County, was discovered by the Continental Oil Co. et al. The discovery well, J. S. Todd No. 2, set. 29, block WX1 G.C. & S.F. R.R. Co. survey, was completed on April 3, 1940. The top of pay was encountered at 5623 ft., and the well was bottomed at 5691 ft. for initial production of 1613 bbl. of 40.6&apos; gravity oil flowing naturally through 2-in. tubing. The pay section was found in Strawn lime of Pennsylvanian age. There were six producing wells in the field at the end of the year. This appears to be another major discovery in 1940. There was no pipe-line outlet in the field at the end of the

Jan 1, 1941

By G. Thodos, R. B. Grieves

A method has been developed For predicting the critical temperatures and critical pressures of binary mixtures of carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen with the normal paraffin hydrocarbons. For carbon-dioxide and hydrogen-sulfide systems, relations are presented that take into account the peculiar behavior of mixtures with closely boiling components, such as carbon dioxide-ethane and hydrogen sulfide-propane mixtures which exhibit minimum critical temperature points. For hydrogen, nitrogen and carbon-monoxide systems, the extreme critical behavior caused by wide differences in pure component properties is established In addition, those fixed gas-paraffin systems which resemble paraffin-paraffin systems are also accounted for. For a mixture of known composition, the pure component critical temperatures, critical pressures and normal boiling points are all that are required to determine its critical point. Graphical relations are presented relating Tc and PC , of the mixture to the pure component properties. From the treatment of 12 carbon-dioxide and hydrogen-sulfide systems reported in the literature (74 mixtures), the expected error lor the critical temperature is approximately 1.5 per cent, and for the critical pressure, approximately 2 per cent. From the treatment of six hydrogen, nitrogen and carbon-monoxide systems reported in the literature (30 mixtures), the expected error for both the critical temperature and critical pressure is approximately 2.5 per cent. The relationships, which have been developed with only normal paraffins as the hydrocarbon components, may be extended to those isoparaffins and olefins which fall within the allowable volatility ranges. INTRODUCTION Many of the fixed gases — carbon dioxide, hydrogen sulfide, nitrogen, hydrogen, carbon monoxide and oxygen — occur in natural mixtures with hydrocarbons. Carbon dioxide and hydrogen sulfide are frequent components of the fluids produced from underground petroleum reservoirs. Nitrogen, carbon dioxide and hydrogen sulfide are present in varying quantities in most natural gases and gas-condensate well effluents. Hydrogen mixtures are of considerable interest in many phases of refining processes of petroleum. The determination of the critical temperatures and critical pressures of such mixtures is of value in vapor-liquid equilibrium studies, for the prediction of the characteristics of underground reservoirs, and for reduced-state correlations of PVT, transport and thermodynamic properties. The accurate estimation of the critical point for binary mixtures is an important initial step toward a complete analysis for the establishment of the critical temperatures and pressures of multi-component mixtures. Methods for predicting the critical temperatures and critical pressures of binary hydrocarbon systems have already been presented in the literature.8 It is possible to apply these existing methods to fixed gas-paraffin mixtures, but due to their unusual critical behavior, values calculated deviate considerably from experimental values. For systems containing trace quantities of the fixed gases, these methods are acceptable; however, for systems containing more than 5 mol per cent of the fixed gases, these utterly fail to produce reasonable critical values. Consequently, in this study a method has been developed for handling such binary mixtures over the entire composition range. CARBON-DIOXIDE AND HYDROGEN-SULFIDE SYSTEMS The critical behavior and the vapor pressure behavior of mixtures of carbon dioxide and hydrogen sulfide with paraffinic hydrocarbons may be quite similar or quite dissimilar to that of paraffin-paraffin mixtures, depending on the volatilities of the components involved. The critical temperature and normal boiling point of carbon dioxide are very close to the corresponding values for ethane, while its critical pressure is considerably higher than that of ethane. The normal boiling point of

By W. I. Duvall

A brief review of the resonant frequency and ultrasonic pulse methods for obtaining elastic constants of rock samples shows that the equations for an iso-tropic elastic solid commonly used to calculate Young&apos;s modulus, modulus of rigidity and Poisson&apos;s ratio can result in appreciable error if the rock is even slightly anisotropic. Consideration of the equations that relate bar velocities and free medium velocities to elastic constants for orthotropic, transversely isotropic and isotropic solids shows that a combination of the two methods can be used to determine average elastic constants for a single sample of rock. The determination of elastic constants in different directions requires a large number of tests on oriented samples. The use of both the resonant frequency and ultrasonic pulse methods is recommended so that the determination of both Young&apos;s modulus and modulus of rigidity is independent of the determination of Poisson&apos;s ratio. The dynamic elastic constants of rock can be determined in the laboratory from measurements on small samples which may be in the form of right circular cylinders (diamond drill core). Either the resonant frequency6 or ultrasonic pulse method1 can be used to determine the longitudinal and shear velocities in the same specimen. The resonant frequency method provides a measure of the longitudinal bar velocity, V,, and the torsional bar velocity Vt; whereas the ultrasonic pulse method provides a measure of the free medium longitudinal velocity, Vp, and the free medium shear velocity, V, . The elastic constants (Young&apos;s modulus E, modulus of rigidity G, and Poisson&apos;s ratio v) are calculated from the density of the specimen, p, and one of the pairs of velocities by means of equations from isotropic elastic theory. For the resonant frequency method the equations are: It should be noted that Eq. 5 is derived from Eq. 4 and 6 and the relation between the elastic constants for an isotropic solid as given by the first part of Eq. 3. The in situ determination of dynamic elastic constants is accomplished by generating a complex seismic pulse in the rock and measuring the arrival times for the longitudinal and shear phases of the pulse at two distant points.5 From these travel times and the distance of the travel path both Vp and Vs are determined. The density of the rock is determined from samples in the laboratory, and Eq. 4 to 6 are used to calculate the elastic constants. These three methods involve the assumption of isotropy and perfect elasticity, and require the use of the relation v = (E/2G) - 1, which holds only if the elastic constants are the same in at least two directions. The calculation of v by means of Eq. 3 introduces considerable error, as a 1% error in V, and V, results in a 20% error in v. If frequencies for samples with a length-to-diameter ratio greater than four and a length greater than 8 in. are measured carefully, the experimental error can be kept to 1%. However, it is not unreasonable to expect that the variation in Vb and Vt with direction may exceed 1%. Thus, for even a small percentage of anisotropy the use of Eq. 3 can result in considerable error in v. The calculation of v by Eq. 5 also involves some uncertainty as a 1% error in Vs and Vp can result in a 6% error in v. By means of the pulse method both

Jan 1, 1965

By C. D. Cochran, F. H. Deily, M. M. White, Victor Horner

A laboratory study of the effects of physical and easily measured rheological properties upon dynamic filtration was carried out. The purpose was to determine the factors affecting dynamic filtration and thus learn how to control this important property. The recommended procedure for determining the amount of fluid loss prescribed by API Code RP 29 "Field Procedure for Testing Drilling Fluids,"&apos; is very useful for mud conditioning purposes, but inadequate for comparing filtration properties of different muds under dynamic conditions. Where dynamic filtration control becomes important for purposes such as logging and coring, other means of evaluating filtration properties are needed. A special device and testing technique were developed to provide reliable data on filtration characteristics of different fluids under dynamic conditions. Liquid saturated rock samples were drilled with a microbit, and the amount of connate liquid displaced by the fluid being investigated was measured. The empirical testing procedure was considered reliable. A large number of laboratory-prepared and field-mixed dritling fluids with a wide range of physical properties were studied. These properties included: (I) shape of consistency curves, (2) apparent viscosity, (3) plastic viscosity, (4) yield value, (5) density, and (6) API filter loss. Test results indicate that very little, if any, trend could be established between changes in these fluid properties and dynamic filtration. INTRODUCTION During the process of drilling, excessive loss of liquid from the mud to the formation is undesirable for many reasons. Filtration can reduce production-zone permeability, cause sloughing of formations, affect electric log curves, and render the fluid data obtained from cores unreliable. Thus, it is very important that we gain a knowledge of the factors that control filtration. It is generally agreed that in any type of filtration (static, dynamic, or combinations thereof), the mechanics of filtering depend in great part upon the composition of the fluid. Moreover, it is also true that the physical and rheological properties are influenced by the composition of the fluid. Indirectly, then, it was hypothesized that a relationship existed between dynamic filtration and physical-rheological properties, two effects of a common cause—fluid composition. This paper discusses an attempt to relate filtration-while-drilling to physical and easily measured rheological properties. It is believed that the results of this study may prove useful to others in the industry who are working on the problem of understanding filtration. The industry accepted practice for determining fluid loss from drilling mud is described in API Code RP 29. The practice is to measure the amount of filtrate that passes during a given interval of time from a quiescent drilling fluid under applied pressure through a piece of filter paper. This is primarily a test of static filtration properties. Other investigators have studied filtration under dynamic conditions. Williams5 and Pro-kop5 studied radial filtration and filter-cake buildup by circulating fluid through a porous cylinder under conditions similar to actual mud flow. Nowak,4 Krueger,3,4 and Vogel3 studied the effect of filtration upon permeability by flowing mud past the face of rock Samples. In their tests, the bit action was simulated by mechanical scrapers that kept the filter cake from building up. Ferguson and Klotz2 studied three types of filtration: static, dynamic, and beneath-the-bit. They investigated each type separately, using a model well in which bottom-hole hydraulics and mechanics were closely approximated.

Jan 1, 1958

By P. Chiotti, E. R. Stevens

The electromotive force between pure magnesium and Mg-Zn alloys in a fused KC1-LiCl-MgC12 cell was measured over the temperature range 360° to 730°C and for alloy compositions of 0.052 to 0.635 atom fraction magnesium. The calculated activity coefficients of magnesium in the liquid alloys may he represented by the relation These data and the phase diagram were employed in calculating the standard free energy of formation for the compounds MgZn, MgZn2, and MgZn2, In the temperature range from 25° to 590°C the relation ZINC-rich magnesium alloys have been shown to be very effective in reducing various solute chlorides or oxides from fused salts such as KC1-LiC1 eutectic. Such reactions are of interest in the developinent of pyrometallurgical methods for reprocessing nuclear reactor fuels.&apos; As the conceniration of the magnesium is increased beyond 5 to 10 wt pct the extent to which solutes, such as yttrium, lanthanum, cerium, and other rare earths, can be reduced or removed from the salt decreases. This effect is due to the resulting change in the activity of the solutes in the Zn-Mg alloy as well as the change in the activity of both the zinc and mag- nesium. The purpose of the present investigation was to determine the thermodynamic properties of the Zn-Mg system which, in addition to yielding information on the alloying behavior of these two elements, would permit a more quantitative understanding of the above reactions. Since this investigation was initiated several publications have appeared in the literature giving results on the thermodynamic properties for the liquid alloys of this system. 2-4 Kozuka, Moriyama, and Kushima3 measured the vapor pressure of zinc over four different alloy compositions by a carrier-gas technique. Eremenko and Tukashenko2 and Terpilowski4 measured the electromotive force between pure magnesium and various alloys in a fused salt cell. Earlier work has been summarized by Hultgren, Orr, Anderson, and Kelley.5 In the present investigation electromotive-force measurements were made on a cell of the type The temperature range covered for the lower-melting alloys was roughly 375° to 730°C. These data were employed in calculating the thermodynamic properties for the liquid alloys and in conjunction with the phase diagram,&apos; reproduced in Fig. 1, were used in calculating the standard free energy of formation of the compounds MgZn, MgZn2, and Mg2 Zn11. The results obtained are compared with available data from the literature. MATERIALS AND EXPERIMENTAL PROCEDURES Materials employed were: Bunker Hill slab zinc, 99.99 pct pure; Ames Laboratory magnesium containing 13 ppm N, 195 ppm C, and trace amounts of calcium, copper, nickel, and silicon; reagent grade KC1, LiC1; and high-purity MgC12 obtained from Dow Chemical Co. The electrolyte consisting of KC1-LiCl eutectic (44.4 wt pct LiC1) to which was added 15 wt pct MgCl2, was dried in a quartz tube by heating to 340° C under vacuum for a period of 4 to 5 hr, and then passing HC1 through the salt as the temperature was slowly raised to above the melting point of the salt. After about 3 hr the HC1 was shut off and the system flushed with argon and then vacuum applied for 1 hr. The salt was finally siphoned through a sintered glass filter and cast into a Pyrex container which was sealed and

Jan 1, 1965

By Nicholas J. Grant, Hanna Ibach, Bill C. Giessen

The system Ta-Rh was investigated over the entire comnposition range using metallogvaphic and X-ray techniques as well as thermal analysis. Terminal solubility limits, solidus temperatures, and the crystal structures of two new intermediate phases were determined. There are five intermediate phases: o, tetragonal, isostructural with o(Fe-Cr); a1, orthorhomnbic : a2, orthorhombic, isostructural with CozSi; 0 3, a high -temperature phase of unknozun structure; and a TaRh3, cubic, AuCu3 structure. a, aL, a,, and a melt peritectically; and a TaRh, has a maximum melting point. Five peritectic and one eutectic reactions occur. THE Ta-Rh phase diagram has not been fully treated in the literature; however, two inter metallic phases have been described.&apos;-&apos; This study attempts to work out the diagram covering the details of phase boundaries as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by National Research Corp., Cambridge, Mass., and rhodium powder of 99.9 pct purity, supplied by Bishop Co., Malvern, Pa. Analyses as given by the manufacturers are presented in Table I. In addition to the spectroscopic analysis, an oxygen analysis has been made of the tantalum powder. After preliminary trials, the standard procedure employed in making the alloys was as follows (see Ref. 4 for further details). The powders were weighed, mixed manually, compacted under 16,000 psi, and arc-melted at not more than 500 amp under thoroughly titanium gettered welding-grade argon of 400 mm Hg pressure. The gettering process was repeated after each melt. It had been shown previously5 that under these conditions no oxygen pick-up exceeding 0.001 pct in a hafnium button could be detected. The buttons, ranging from 5 to 10 g in weight, were inverted or, if possible, crushed and remelted three times. Melting presented no difficulty, except for tantalum-rich al- loys, which showed considerable spashing during melting. The average weight loss of 1 wt pct rose to 2.5 wt pct in these cases. Subsequent melting, however, resulted in losses of less than 0.1 wt pct. The melts obtained frequently showed small in-homogeneities, mostly in the tantalum-rich part of the system below 25 at. pct Rh. This was not due to insufficient blending of the elements, but to crystallization taking place from the cooled bottom. This condition was not improved by further re-melting; therefore the following precautions were taken. Cross sections of as-cast buttons were made. For the investigation only buttons were used where these inhomogeneities did not exceed 1 at. pct (estimated from the amounts of haSeS resent). In addition, only the center portions of such buttdns were utilized to minimize errors. Smaller buttons showed smaller concentration gradients and were used as a check. Finally, all alloys were homogenized to eliminate coring (see below). After this, the error in alloy composition due to inhomogeneity was cl at. pct. In order to confirm the concentrations of the alloys and to provide an impurity check, wet-chemical analyses and oxygen-fusion analyses of four key alloys were carried out. The results, together with the concentrations as calculated with the weight balance method, are presented in Table 11. It was found that for three alloys the agreement is very good (< 0.2

Jan 1, 1964

By B. C. Craft, Murray F. Hawkins, John R. Rayne

A reservoir mechanism of sulfur recovery by the Frasch process is presented. Improving the economic, of recovery appears to be largely a well, rather than a reservoir problem. A most important factor is the limitation of the lateral extraction of .sulfur about the wells due to the almost vertical .flow of the injected hot water. Model studies are described which confirin the mechanism of sulfur recovery by presently used methods. Studies on a five-spot system indicate improved econo171ics regarding recovery, recovery rate, therinal efficiency, and well spacing. INTRODUCTION Sulfur mining by the Frasch process is one of the most important methods of sulfur production. Developed by Herman Frasch in 1894, it enjoyed a rapid growth and presently supplies 40 per cent of the world&apos;s sulfur and about 80 per cent of the U. S. sulfur." The Frasch process of mining the underground native sulfur deposits involves melting the sulfur in place by introducing super-heated water into the sulfur bearing formations, and producing the sulfur as a liquid. Many problems are encountered in mining these native sulfur deposits, and sulfur production depends chiefly upon the nature of the sulfur deposit and the underground thermal efficiency of the heat transfer system. THE RECOVERY MECHANISM Sulfur is typically found in salt dome cap rock as crystal aggregates occurring within the cavities, seams, and pores of limestone and gypsum formations.&apos; Sulfur-bearing limestone is typically cavernous, vugular, and fractured. Porosity averages about 20 per cent and sulfur saturation averages approximately 25 per cent by weight.1,15 Vhe sulfur bearing formations are very heterogeneous in nature and physical characteristics vary widely within small distances. Total cap rock thickness may vary from 50 to more than 1,000 ft, and net productive thicknesses from a few feet to a few hundred feet. In most cases the upper portion of the limestone formation is barren of sulfur, varying from 5 to 200 ft in thickness.1,15,33 The immediately overlying sediments and the underlying dense anhydrite formation provide permeability barriers to the flow of water from the cap rock section.&apos;" Sulfur wells are drilled with conventional oilfield drilling rigs. Fig. 1 illustrates the casing program of a completed sulfur well. The cap rock sections are drilled with core bits and continuous core logs are recorded. After coring, the cap rock section is underreamed to a diameter of 9 7/8 in. The bottom of the 8-in. casing is welded closed and rests on the bottom of the drill hole, which extends through the cap rock to a few feet above the bottom of the sulfur-bearing formation. The 8-in. pipe contains 5 ft of 3/4-in. perforations on 6-in. centers and 15 ft of 1-in. perforations on 1-ft centers. The 20-ft perforated section is set opposite the lower 20 ft of the sulfur-bearing formation. The 4-in. sulfur pipe is set inside the 8-in. water line on a seat ring at the top of the 5-ft section of 3/4-in. perforations. The mining water, heated to about 330°F under a pressure of 250 psi, is forced down the annulus between the 8-in. and 441-1. pipes and through the 1-in. perforations to the sulfur-bearing formation. Compressed air, at 400 psi pressure, is supplied through a 1-in. air line near the bottom of the well to provide air-lift of the liquid

Jan 1, 1957

By C. A. Hartnagel

During- the past 10 years the annual production of petroleum in New York has averaged close to 5,000,000 bbl., the total for the period being 49,881,000 bbl. In 6 of the 10 years, the production was slightly in excess of the 5,000,000 mark. The 1944 production of 4,697,000 bbl. represents a 7 per cent decline from the previous year. Of the total 1944 output, the Allegany County district, which includes two small areas of Steuben County, contributcd 3,614,065 bbl., a decline of 5 per cent from 1943, and the contribution of Cattaraugus County, which represents the northern extension of the Bradford pool of Pennsylvania into New York was 1,082,935 bbl., a decline of more than 14 per cent. Since March 1942, the posted price of New York crude oil has remained at $3.00 per bbl. On lug. I, 1944, a Federal subsidy of 75¢ per bbl. was granted to oil producers, thus making the price actually $3.75 per bbl. Since all of the oil produced in New York comes under the designation "stripper well operations," it is entitled to the Federal subsidy. During the last few years there has been little change in the number of wells drilled annually. In the Allegany field, which accounts for three fourths of the oil produced in the state, 1240 wells, including water-intake wells, were drilled during 1944 as compared with 1223 in 1943. There was no marked increase in the number of wells drilled after granting the subsidy of 75¢ per bbl. of oil on Aug. I, the increase being but 14 wells during the last half of the year over the preceding six months. In flooding operations it is not to be expected that even a substantial increase in the price of crude oil will be reflected quickly in an increase of the number of wells drilled or in a marked increase in production of crude oil. In flooded areas, oil is obtained through a program extending over a number of years. This program involves the drilling of the water or input pressure wells, drilling of the oil wells, building up the oil flood to maximum production, and finally the watering out of the well when the amount of oil produced in proportion to the water becomes so small that pumping is no longer profitable. The various operations may extend over a period of 10 years or more, during which time the price of crude may have fluctuated greatly. Although the rate of production can be controlled to a limited extent, it is evident that a flood when once begun must be continued regardless of the price of crude. During the past seven years New York crude has had a price range from $1.68 per bbl. in 1938 to the present price of $3.75 per barrel The field pattern now in general use for wells in a flood project is the "five-spot." Under this arrangement, the lease is divided into squares with a water well at each corner and an oil well in the center. In the all-over pattern of the lease each oil well is acted upon by four water wells and each water well supplies part of the pressure to four oil wells. Spacing between the input water wells and the oil wells usually varies from zoo to 225 ft. or, on an acre basis, there is one oil well and one water well for each 2 1/2 acres. In recent years there has been a tendency to increase

Jan 1, 1945

By A. M. Gaudin, D. W. Fuerstenau

IN concentration of certain ores by soap flotation, prevention of quartz flotation is desired; the contrary is true in treatment of some oxide iron ores. Experimental study of the flotation of quartz goes back at least a quarter of a century.&apos; Clean quartz does not float with fatty acids or soaps but does float when activated by one of many metallic salts. Control of pH is important. Broadly speaking the problem of quartz flotation has been approached from the empirical side, as was the related topic of flocculation or dispersion of quartz suspensions? Empirical studies indicated the existence of critical relationships between the additions of collector and activator. These additions were not stoichiometric for the formation of soaps of the activator cation. For example, Gaudin and Rizo-Patrona found optimum quartz flotation at pH 10.6 using barium activation and oleate collection when the molar ratio of oleate to barium was 1 to 1 instead of 2 to 1, as would be called for formation of Ba(OL),. Cooke and Digre" &apos; found that if calcium is the activator, a minimum quantity of that agent is required for effective flotation when the pH is 11.5. In other words, if the concentration of Na&apos; exceeds 10 -2.5 mols per liter or if the concentration of H exceeds 10-11 mols per liter, the concentration of Ca++ in solution required for quartz activation is increased. This suggests that H+ is much more effective than Na+ on 10-2.5 quartz, perhaps in the ratio ofp or 108. Schuh- mann and Prakash6 studied anew the activation of quartz by barium, calcium, aluminum, and ferric iron. Salts of these metals are activators provided they are in stoichiometric excess over the collector used with them. Alkaline-earth salts are effective only in alkaline circuits. Important as they are in giving data on the effect of various agents on quartz, all these studies fail to give information on the detailed structure of the quartz-solution interface. A beginning in this direction was made by Gaudin and Chang,? who measured the adsorption of radioactively marked barium and laurate ions at quartz surfaces, and by Gaudin. Spedden, and Laxen,8 ho measured the adsorption of radioactively marked sodium at quartz surfaces. Work has also been done by Bell0 n measurement of the adsorption of sodium ion and chloride ion at quartz-solution interfaces. In all these experimental measurements of adsorption, the solid was centrifuged or filtered from the bulk of the liquor with which it had been associated; and the composition of the solid surface was ascertained by analysis, after allowance was made for the ionic composition of the liquor included with the centrifuged solids on the assumption that it is identical to the bulk liquid. Adsorption measurements give only the total amount of collector adsorbed at the quartz-solution interface; they give no indication of the distribution of these adsorbed ions at the interfacial layer. It is the ionic structure of the solid-solution interface and its importance to flotation that is the subject of this paper. The structure of this interfacial layer can be investigated by means of electrokinetic methods so that by combining electrokinetic studies with adsorption measurements, a more complete picture of the quartz surface may be obtained. The following studies were made to ascertain how electrolytes used in the soap flotation

Jan 1, 1956

By P. Dayal, L. S. Darken

THE migration of carbon in austenite under the influence of an electric current has been observed qualitatively several times.14 Lebedev and Guterman5 recently have reported quantitative measurements; their method consisted of welding a low-carbon to a high-carbon wire, passing current, and later estimating the carbon distribution metal-lographically. We believe the method reported in this paper is superior in principle since electrolytic migration and ordinary diffusion are not necessarily coupled as in the weld method; also for the first time the extent of migration is determined by combustion analysis for carbon. A uniform tubular specimen (S.A.E. 1045 or 1095) was mounted as illustrated in the figures. the whole assembly being in an atmosphere of purified nitrogen. Direct current (129 to 226 amp at 0.65 to 1.0 v) served as source both of heat and of potential gradient for carbon migration. The duration of experiment was 7.5 to 12 hr, during which time the temperature was controlled (±10°C) manually. The experimental conditions are indicated in the first five columns of table I. With this experimental arrangement, the temperature initially has a maximum value at the central plane. Also, in this vicinity (by virtue of the symmetry), the carbon entering any volume element is equal in quantity to that leaving; the loss or accumulation of carbon occurs near the electrodes since the carbon moves uniformly near the center and is "frozen" at the cold ends. Hence, providing the time of experiment is not sufficiently long to seriously influence the conditions at the central plane, carbon crosses this plane only under the influence of the electrical potential gradient and not under the influence of temperature or concentration gradient. The amount of carbon which has crossed this plane was determined by combustion analysis of the two halves of the specimen. The results of these analyses are shown in the sixth and seventh columns of table I. It will be noted that substantial amounts of carbon migrated from the anode portion to the cathode portion (except at 920°C, which temperature was too low to exhibit the effect in the allotted time). In spite of precau-tions taken, considerable decarburization occurred as may be seen by comparing cols. 8 and 5. In three cases (indicated by asterisks in table I) the specimen was ground on one side, polished, and examined metallographically before analysis. One specimen was normalized and re-examined. Micrographs of selected areas in specimens 4 and 6 are shown in figs. 1 and 2, respectively. Evidence of carbon migration from the anode toward the cathode is quite apparent. Fig. 2 shows abundant graphite as well as cementite in a region near the cathode. The temperature of this zone is estimated at about 800°C. In fig. 1, particularly in the micrograph on the extreme right (the right side of which is of unaltered carbon content), there is evidence of slight depletion of carbon in the immediate vicinity of the cathode as contrasted to the general increase in carbon of the cathode half of the specimen. Although this may be attributed in part to decarbur-ization, it is believed that it is occasioned also by thermal diffusion—migration (of carbon) from a cool to a hot zone4—a phenomenon superimposed upon the electrical migration. Evidence of carbon migration was visible particu-larly during the course of the high-temperature,

Jan 1, 1951

By F. H. Buttner, E. R. Funk, H. Udin

Gold wires, 5 mil in diam, are found to creep viscously up to approximately 5.5x106 dynes per sq cm around 1300°K. Beyond this point, an additional slip mechanism appears. The average coefficient in the viscous range at these temperatures is 18.9 ± 7x10 12 poises. This observation and other visual observations made during the experiments agree with Herring&apos;s predictions. EARLY creep studies by Chalmers on single crystals of tin produced some of the first experimental evidence to suggest that metals deform viscously under very light stresses. That is to say, over a small initial stress range up to 150 g per sq mm, the single crystals of tin elongated at a rate proportional to the stress. The proportionality constant between strain rate and stress is by definition the coefficient of viscosity. Chalmers named this range of proportionality the microcreep range. One of the first theoretical attempts to explain the microcreep phenomenon was given by Kauzman,&apos; who applied Eyring&apos;sQ eneral statistical mechanical theory of shear rates to creep data then available. From the rate theory, he deduced the general hyperbolic sine law for shear rate on the assumption that the distortion of the reaction path due to stress is negligible and that the system is an infinite continuum. In order to fit the available data to the equation, it was necessary to assume that creep occurs by shear of rather large blocks of material, rather than by an atomistic shear process as in diffusion. The size of the shear units was shown to increase with increasing temperatures and lower stress, or lower strain rates. In applying the hyperbolic sine law equation to the microcreep data of tin, it was shown by Kauzman that the unit shear blocks became quite small, which suggested to him that microcreep might be a self-diffusion process. Making this an assumption, Kauz- man reworked the rate theory and arrived at an equation where the shear rate is proportional to the stress. In the form of viscosity coefficient, the equation is: o- _ \LkT V = 2qAlA where u is the stress; S, the shear rate; X, the distance in shear direction moved by flow units relative to one another in the unit process; L, the distance between layers of units of flow; T, the absolute temperature; k, Boltzmann&apos;s constant; qAL, a constant proportional to the size of flow units; and kT A, the diffusion coefficient = ------kTe-Q/RT = K X2 h Kauzman applied the expression to molten lead with a fair degree of success, the calculated viscosity being low by a factor of four. For solid lead the result is 5000 times too high. Taking q = 1, and X = dA = L = 21 = nearest neighbor distance, Udin, Shaler and Wulff8 found the equation low by a factor of lo7 for solid copper. On the basis of the discrepancy in lead, Kauzman indicated that microcreep is probably not a simple diffusion process of molecular shear units, but one involving preferential diffusion paths, or even that diffusion in solids does not involve shear at all. Cottrell and Jaswon4 treat the microcreep phenomenon on the basis of slow moving dislocations and apply it to Chalmers&apos; data on tin with fair success. Nabarro Suggested a microcreep model in which mass movement in the direction of pull is effected by the diffusion of holes. The tension on the crystal effectively creates a greater hole concentration at regions near the crystal surfaces perpendicular to

Jan 1, 1953

By Leonard R. Weisberg

HE procedure of directional freezing by the Bridgman technique1 is frequently used in crystal preparation. On those occasions where the crystal is regrown, it can be advantageous to Crop part of the ingot before regrowth to achieve purification. This note describes some simple, yet interesting, observations concerning the effects of cropping an ingot between successive freezes. First, it is not effective to Crop the front end of an ingot, whether or not the distribution coefficient, k , of the impurities is greater or less than unity. This can be shown as follows. The concentration C, of an impurity in a directionally frozen ingot of length d with a uniform cross section is given by where x is the distance along the ingot, and C0 is the initial concentration per unit length. It is assumed in deriving this equation that diffusion is negligible in the solid, is complete in the melt, and that k is constant. Consider that a section of the ingot Ad is removed from the front end. Then the average impurity concentration in the remaining (d- Ad) section of the ingot can be shown by integration to be given by When the ingot is remelted and refrozen, the new impurity distribution is given by where xl is the distance along the refrozen ingot. Substituting the value of c into Eq. [3], one finds This is identical to Eq. [11 when x = (x, Ad), which represents the original impurity distribution in the (d - Ad) section of the ingot after the first directional freeze. Therefore, the cropping and re-freezing accomplished nothing. This can also be seen physically by realizing that the average impurity content in the melt after the first Ad section is frozen, is identical to that after the resulting ingot has been cropped and remelted. Hence, it is assumed in the following sections that only the tail end of the ingot is cropped. However, it must be realized that for impurities with k greater than one, the pieces cropped from the tail end are purer, and are therefore saved. After cropping an amount Ad from the tail end of an ingot, the average impurity concentration of impurities in the remaining portion of the ingot is given by wheref= d/d. For the case of k < 1, the purification is defined as c,/c. It is obvious from Eq. [5] that the purification increases asf increases, but the increase in purification is not large. For example, iff is doubled from 0.1 to 0.2, the purification increases by only 10 pct for k = 0.5, by only 24 pct for k = 0.1, and by 32 pct for k =0.01. Much smaller values off than 0.1 are not desirable since insufficient purification is achieved. These figures indicate that much larger values off do not lead to substantial improvement, especially considering that much of the original ingot is lost. Therefore, it is generally useful to Crop about 1/10 of the ingot to achieve purification. As compared to doubling the value off, it is much more helpful to remelt, refreeze, and crop the ingot twice. Using Eq. [51 reiteratively, and assuming f= 0.1, it is found that the purification after this process is found to be increased over the purification after a single freeze and cropping by 33 pct for k= 0.5, 450 pct for k = 0.1, and 4100 pct for k = 0.01. This indicates that considerable purification can be obtained by this procedure. However, if purification is the main goal, one should resort to zone refining,3

Jan 1, 1962

By Fred D. Gustafson

With the postwar emergency for new housing and for new industrial buildings, much research has been done on lightweight aggregates for use in concrete and plaster. The trend toward lighter weight aggregates to relieve the dead load on the higher, steel framework buildings started toward the end of the last century. Progressively the requirements became more stringent, crushed bank slag, weighing 80 lb per cu ft as compared to 100 lb for crushed rock, was supplemented in some sections by foamed slags and expanded shales weighing from 40 to 60 lb per cu ft. In other sections cinders were used weighing from 40 to 50 lb, including sand. Sections favored with more recent vulcanism turned to pumice weighing from 30 to 60 lb, whereas other localities made use of diatomite, from 28 to 40 lb. Exfoliated vermiculite weighing from only 6 to 10 lb per cu ft came into use. As the search for lighter weights in aggregates continued so did the search for other desirable properties such as nailability, ease of cutting or channeling, and good insulation to both sound and heat. This search eventually led to a widespread interest in the expansion of perlite, or similar volcanic glasses, with the result that in 1946, the Office of the Housing Expediter&apos; listed eleven firms reporting the operation of processing plants either on pilot or commercial scale producing aggregates weighing from 2 to 16 lb per cu ft. Geology Perlite is one of the large family of rocks originating from a granitic or acidic magma and generally has a "rhyolitic composition with a marked perlitic structure."² The name "perlite" is a derivation from "perlstein" originally given "to certain glassy rocks (hyaloliparites, hyalo-rhyolites) with numerous concentric cracks, from the fancied resemblance of broken out fragments to pearls."3 The cause of the perlitic texture is somewhat controversial. Johannsen attributes the texture to strain set up in the glass by cooling and describes the finding of peculiar, glassy balls, called marekanite, more or less rounded and showing concave indentations, which may be left when perlite is broken. Frank Rutley, on the other hand, in 1881, while working on vitreous rocks from Montana, observed that there was incipient or partially started crystallization with segregation of water toward the un-crystallized portion in all specimens of perlite examined. Further he observed evidence of strain around focii of crystallization to which he ascribed the development of the spherical cracking which gives the rock its perlitic texture.4 Widespread over the western and southwestern United States where Tertiary vulcanism is exposed, perlite commonly is associated with andesitic, basaltic, and rhyolitic lavas with inter-bedded tuffs and ash of Eocene age although some deposits are associated with rocks assigned to the Pliocene age.5, 6 n nearly all cases the perlite overlies water laid tuff beds or agglomerates or breccias of explosive nature, an outstanding exception being the occurrence of perlite as the chilled selvage of andesite intrusions.7&apos;8 Available chemical analyses of per-lites from the western and southwestern United States indicate that they are varieties of leucorhyolites rather than of normal rhyolites, leucorhyolites having less than 5 pct of dark minerals, normal rhyolites having more than 5 pct. This conforms with Johannsen&apos;s observation that leucorhyolites are the prevailing kind in North America.9 Tables 1 and 2 give

Jan 1, 1950

By G. F. Sager, B. J. Nelson

Magnesium alloy forgings offer higher and more uniform mechanical properties than heat treated magnesium alloy castings and are used principally for light weight parts that may be stressed in fatigue or subject to impact loads, or where space limitations do not permit the use of the necessarily bulkier magnesium alloy castings. Compositions and Properties of Magnesium Forging Alloys The nominal compositions and properties of the principal commercial magnesium forging alloys are given in Table 1. The two that are most commonly used are AMC58S and AM65S. The former has the highest strength and is, therefore, employed for heavy duty applications. However, the forging of this alloy and of AMC57S ordinarily requires the use of slow speed hydraulic presses. The forging alloy AM65S combines good, although somewhat lower, mechanical properties with excellent forging characteristics. This alloy can be forged on hammers, upsetters, rolls, and mechanical presses, as well as on hydraulic presses. These characteristics make it particularly useful for many applications. Manganese Segregation in AM65S The alloy AM65S contains 5 pct tin, 3 1/2 pct aluminum, and a small amount of manganese, the manganese being added to insure satisfactory resistance to corrosion. Some manganese segregation was occasionally encountered in this alloy. In many applications, such segregation is of no particular consequence, but when forgings are acid dipped prior to the application of various chemical coatings, the segregated particles of manganese constituent may stand in relief. The resultant surface roughening may impair appearance and is undesirable in forgings employed in the textile industry, where very smooth surfaces are essential to avoid the catching and breaking of fine threads. An effort was therefore made to determine the cause of manganese segregation in this alloy and find a method for its elimination. Radiographic examination of a series of cast ingot sections and extruded samples of the AM65S type having manganese contents ranging from zero to about 0.7 pct revealed no appreciable manganese segregation when the manganese was less than about 0.4 pct. A small amount was observed with a manganese content of 0.46 pct and considerable with manganese contents of 0.6 pct or higher. Attempts to eliminate the manganese segregation by variations in the melting and casting conditions were unsuccessful and it soon became apparent that the trouble was attributable to the fact that the manganese contents that caused segregation were in excess of the amounts that would remain in solution at temperatures encountered in the melting and/or casting operations prior to the complete solidification of the ingots. A knowledge of the amounts of manganese that would be soluble in molten alloys of the AM65S type at various temperatures was obviously desirable. The liquid solubilities of manganese in binary Mg-Mn alloys and in Mg-Al-Mn and Mg-Zn-Mn alloys have been determined by Tiner and others,* but no data on the solubility of manganese in molten magnesium alloys containing tin and aluminum are given in the literature. For this reason, an investigation to determine the solubility of manganese in a magnesium alloy containing 5 pct tin and 3.5 pct aluminum (AM65S type) was undertaken.

Jan 1, 1950

By J. E. Gruzleski, O. Knacke, M. J. Meixner

The evolution of CO from small specimens of solidifying steel was investigated using a thermobalance technique. Gas evolution begins in the temperature range between 1400" to .1450°C. This behavior is independent of the initial carbon content and the cooling rate. At a constant temperature above 1220°C, the rate of gas evolution is temperature independent. Out-gassing of the specimen is thought to proceed through small channels formed by the coalescence of bubbles between dendrites. LIQUID metals have a higher solubility for gas than the solid. During freezing, these gases form bubbles which may either escape or remain trapped in the solid. Recent work1 on the evolution of oxygen from solidifying silver showed that the gas is not liberated until a large fraction of the melt has solidified, and that the gas is evolved in an almost explosive manner. Because of the commercial importance of CO evolution in solidifying steel, a similar investigation was undertaken to study the mechanism of gas liberation in steel. EXPERIMENTAL The thermogravimetric method of Knacke and eixner1 to follow gas evolution by weight changes was employed. Weight differences of 0.1 mg could be reproducibly measured on specimens weighing 2.5 g. These specimens were taken from alloys with varying carbon contents from <0.01 to 0.11 wt pct and <0.01 wt pct of each of silicon, manganese, and aluminum. Specimens contained in 8 mm ID magnesium alumi-nate crucibles were heated to 1550°C under 1 atm of very pure (99.995 pct) CO with a tungsten resistance furnace. The specimen temperature was measured with a Pt-Pt/Rh thermocouple located directly beside the crucible. It is felt that the temperature thus measured was within 5" to 10°C of the specimen temperature since on fusion the weight of the specimen increased due to uptake of CO, and this weight increase was always observed to begin within the temperature range of 1530" to 1540°C. Even after 3 hr there was a small weight increase with time indicating that the molten specimen was not completely saturated with CO. Therefore, complete saturation was not attempted, and all specimens were simply held for 3 hr at 1550°C before cooling. Two types of cooling experiments were performed. One consisted of continuous cooling at linear rates from 5°C to 20°C per min down to 1020°C. The second type of experiment involved continuous cooling at 10°C per min to a predetermined temperature, and then holding the specimen at this temperature for a certain time. During all of these experiments, the sample weight was recorded as a function of time and temperature. OBSERVATIONS Continuous Cooling Experiments. No gas evolution was detected above 1450°C. The initial weight decrease always occurred between 1400" and 1450°C with the average at 1430°C. With further cooling, gas evolution continued to about 1150°C. Between this temperature and 1020°C no further outgassing was observed. This behavior did not seem to depend on the initial carbon content nor on the cooling rate in the range investigated. Typical patterns of gas evolution are shown in Figs. 1 and 2 for different initial carbon levels and cooling rates. The total amount of gas liberated during solidification varied with the rate of cooling. The total weight change on continuous cooling at a rate of 10°C per min

Jan 1, 1970

By E. C. W. Perryman

On electropolishing, high-purity Cu-Sn and Cu-Sn-P alloys with more than 5 to 9 pct Sn were found to contain many grain boundaries with a ridge-and-furrow profile. The effect was not eliminated by solution treatment and was present at the new boundaries in recrystallized material. It could be produced by diffusing tin into the 3 pct Sn alloy and it is concluded that the effect is due to enrichment of certain boundaries in tin, or possibly in an impurity present in the tin, in solid solution. IN the hot working of tin bronzes, especially those with moderately high tin contents, considerable difficulty is frequently encountered from intercrystal-line weakness, which results in cracking at the edges in sheet on strip rolling and in the unsupported regions of the rod in rod rolling.&apos; These difficulties are not at all pronounced with up to 3 pct Sn, but at 5 pct Sn impose serious limitations and at higher tin contents, especially if the phosphorus content is also high, they may become very severe. In some work carried out at the laboratories of The British Non-Ferrous Metals Research Association it was found that a notable lack of ductility in tension at elevated temperatures, associated with intercrystal-line failure, was characteristic of tin bronzes even of relatively high purity. That the intercrystalline fracture is not due to a brittle or molten impurity phase at the grain boundaries was shown by the fact that the temperature at which intercrystalline fracture first occurred decreased with decrease of rate of straining. Tensile tests on some commercial tin bronzes, reported by Goetzel,² show a similar fall in ductility with increasing temperature. As no visual evidence had been obtained showing that the grain boundaries of the tin bronzes were different from those in copper, a more detailed microscopical examination was carried out, and the results of this are given in the present report. Several workers"&apos; have observed that electrolytic polishing is a powerful tool for detecting small amounts of a second phase and in particular for detecting high solute concentrations, "equilibrium segregation," at grain boundaries. Since it had been found that the suggested solutions for electropolishing bronze and the standard solutions for brass and copper did not give satisfactory results it was first necessary to find a suitable electropolishing solution.&apos; Experimental Procedure Materials Used: The cast and wrought materials used for this work were the same as those used for the mechanical tests referred to above. They comprised 3, 6, and 9 pct Sn alloys without phosphorus and the same three basic alloys with 0.03 and 0.4 pct P. A 5 pct Sn alloy without phosphorus, of similar purity, was also examined. The basis materials were Chempur tin, high purity 15 pct phosphor-copper and cathode copper, and spectrographic analyses are given in Table I. Treatment: The cathode copper was first melted under charcoal, degassed by plunging marble chips beneath the surface, and cast through a coal gas flame into sand molds to produce a number of small ingots which after machining were of a suitable size for subsequent vacuum melting. Chill cast bars of the alloys, approximately 1¼ in. in diameter, were then made by melting and casting in vacuo, the tern-

Jan 1, 1954

By W. W. Gerberich

SINCE the original formulation of fracture mechanics concepts,&apos;y2 relatively little work has related the fracture mechanics description of metal behavior on a gross, structural component scale to the behavior of its microstructural constituents. The purpose of this note is to suggest the utilization of fracture mechanics to describe material behavior on a microscopic scale. A Fracture Concept for Two-Phase Structures. A critical displacement concept considering the tough unidirectional phase in a relatively brittle matrix is first examined. It is assumed that a flaw exists at position 1 as depicted in Fig. 1. As the crack moves from position 1 to 2 the plastic zone could be of the shape described with the size approximated by the Dugdale3 model: where c is the half-crack length, OO is the applied stress, and oyS is the yield strength. Hahn and Rosen-field4 have presented a simple fracture criterion for homogeneous materials based upon the displacement at the crack tip. They also have shown the equivalence of the critical displacement, v*, to fracture toughness by Kc = (2v*oysE)1/2 [2] The displacement at the crack tip is given by and the displacement at any distance in front of the crack tip may be determined knowing the plastic zone size and utilizing the development of Goodier and Field.5 Recalling Fig. 1, the value of v* for fracture in material M1 may be calculated from Eq. [2] providing the critical stress intensity factor is known. As the material is loaded, when vc > vM1 the crack moves from position 1 to position 2 where it encounters the tough second phase. If vc2 < vm2, then the crack will be arrested providing the width of the M2 phase is sufficiently large. This condition is necessary since the displacement at position 2 has increased due to the longer crack length. Thus, the displacement at the distance X (representing the dimension of the second phase) in front of the crack may be larger than the critical displacement for failure in the brittle material. If v, > vm, then failure will proceed in the brittle material. The value of v, may be calculated as indicated above. This latter consideration is the same as predicting fracture of a brittle second phase at some distance in front of a crack located in a ductile matrix. Experimental Evidence. On a macrostructural scale, tungsten wires in a ductile Be-Cu matrix are seen to fracture well ahead of the main crack front in Fig. 2. Utilizing a Kc value of 14.2 ksi-in.1/2 obtained by Schroder et al.6 for as-received tungsten, the critical displacement 2v*, for fracture is calculated from Eq. [2] to be about 6.5 X 10-5 in. The crack tip displacement, 2vc, is calculated from Eq. [3] to be 0.0028 in. indicating that fracture would occur at a considerable distance in front of the crack tip. From the ratio of v*/vc and the plastic zone estimate of Eq. [I], the distance in front of the crack tip at which a tungsten wire should fracture is calculated to be about 0.195 in. As shown in Fig. 2, a fractured wire occurs at a distance of 0.140 in. (fractured in three places), not at 0.250

Jan 1, 1968

By T. J. Whalen, S. M. Kaufman

Surface-tension measurements for liquid Fe-C-Co and Fe-C-Ni alloys were performed by the sesszle-drop technique at 1350o and 1425°C. Cobalt was shown to he more effective than nickel in lowering the surface tension of Fe-C alloys A minimum value for surface tension of 1640 dynes per cm was found in the Fe-C-Co system at a concentration of 1.5 pet C and 12pet Co. Analysis of these measurements in terms of adsorption and desorption behavior indicated that cobalt and nickel lower surface tension in Fe-C alloys by replacing carbon at the liquid-vapor interface. Comparison of results to date for Fe-C liquid alloys has shown that most substitutional-type elements having about the same atomic diameter as iron also have relatively the same influence on surface tension when present in dilute amounts. It has been shown previously that surface-adsorption behavior in liquid Fe-C ternary alloys is related to the manner in which the ternary addition affects the activity of carbon in the bulk solution.&apos; Certain ternary additions, such as chromium, tending to decrease carbon activity cause adsorption of carbon and chromium to the liquid-vapor interface. Additions, such as silicon, increase the carbon activity, resulting in a desorption of carbon and an adsorption of silicon. Both cases were shown to cause a decrease in surface tension due to adsorption. It is the object of this paper, as part of the writers&apos; continuing interest in the effect of alloying additions on the surface tension of Fe-C alloys, to present and discuss surface-tension data on solutions in the ternary systems Fe-C-Co and Fe-C-Ni. Available activity measurements for these systems in the solid state indicate a strong increase in carbon activity when either nickel or cobalt is added to Fe-C alloys.2, 3 EXPERIMENTAL PROCEDURE The alloy compositions used are shown in Table I. These alloys were prepared by vacuum melting in stabilized zirconia crucibles and then vacuum casting into cold-steel molds. The nominal analyses for the alloys used in this investigation are given in Table I. Surface tensions and densities were measured by the sessile-drop method4,5 in conjunction with the tables of Bashforth and bdams.&apos; Specimens were prepared by slicing 1/4-in. cubes from the center of the vacuum-cast ingots and grinding the edges of these cubes until their shapes approximated spheres with flat bottoms. Proper handling techniques, including an acetone rinse immediately before use, assured minimum contamination from sources extraneous to the actual melting. For each experimental run a sample was placed on a BeO plaque and positioned and leveled inside a vacuum induction heating apparatus. The sample and plaque arrangement sat inside a molybdenum tube which acted as the susceptor. Diagrams of this apparatus may be found in the literature.= After heating to temperatures just above the liquidus at pressures of the order of 10-4 to 10- 5 mm Hg, photographs of the drop profile were made using its natural thermal radiation as a light source. Some measurements were made with partial pressures (-1 cm Hg) of a mixture of H2 and He gases. The H2-He atmospheres proved to be necessary at higher nickel contents to retard excessive vaporization losses. Chemical analysis for carbon and the ternary addition was performed for each alloy sample after completion of the experimental run.

Jan 1, 1964