Search Documents

By W. D. Robertson, R. E. Reed-Hill

DEFORMATION of magnesium crystals in a direction parallel to the basal plane has a special significance as a result of the preferred orientation characteristic of cold worked and recrystallized polycrystalline magnesium sheet and extruded rod in which the basal plane tends to lie in or near the plane of the sheet or the axis of a rod. The principal objective of the present study is a determination of the modes of plastic deformation in magnesium single crystals in this orientation. Evidence for nonbasal slip in magnesium has been presented by a number of authors. Schmid and Was-serman&apos; indicated that pyramidal slip on {1011} < 1120> or {1012} <1120> could occur above 225°C. Bakarian and Mathewson2 stablished that the slip system {1011} <1120> operates at high temperatures and that 225°C was a lower limit for pyramidal slip. The latter authors also showed that the critical resolved shear stress for {1011} slip was 400 g per sq mm at 330°C, while that for basal slip was 66 g per sq mm at the same temperature. Thus, at 330°C basal slip should be expected for all orientations except those in which the stress axis lies almost in the basal plane. More recently Burke and Hibbard3 oserved pyramidal slip at 25°C, when the stress axis was 6" to the basal plane and 14" to a <1120> slip direction. The critical resolved shear stress for pyramidal slip was 52 g per sq mm, which is only slightly greater than their value for basal slip (46 g per sq mm). Chadhuri, Chang, and Grant4 have observed non-basal slip in creep tests with polycrystalline specimens in the temperature range 250" to 350°C. The observed slip bands, which were extremely irregular in appearance, can be explained in terms of cooperative slip on {1011} and (1010) planes which have a common slip direction. Prismatic (1070) slip in polycrystalline magnesium was observed by Hauser, Landon, and Dorn.5 It was found to occur at low temperatures (78" and 195°K) and it was accompanied by cross slip in which the cooperating plane was the basal plane. Since prismatic slip occurred only at regions of high stress concentrations, the critical resolved shear stress could not be determined. Experimental Procedure The present work was performed on crystal specimens which were all cut from the same large single crystal. The original cylindrical crystal, 0.5 x 7 in., was grown in a Bridgman type furnace in which the temperature gradient was moved past the stationary crystal in the manner described by Jillson6 and Burke.&apos; High purity magnesium was furnished by the Dow Chemical Co. with the following spectro-graphic analysis in weight percent: 0.003 pct Al, <0.01 pct Ca, 0,002 pct Cu, <0.001 pct Fe, 0.008 pct Mn, <0.001 pct Ni, <0.002 pct Pb, <0.01 pct Si, <0.001 pct Sn, and <0.01 pct Zn. The large crystal was cut into four cylindrical pieces about 1.5 in. long. A flat surface parallel to the basal plane was made by hand grinding with lubricated metallographic paper on one side of each cylinder. In order to prevent bending in subsequent cutting operations, the crystals were supported by

Jan 1, 1958

By J. L. Huitt, IM. L. Slusser, E. E. Glenn, M. L. Slusser

This paper is concerned with: (1) an analysis and interpretation of the filtration characteristics of drilling muds on filter paper, and (2) an interpretation of early stage "filtration" on consolidated synthetic porous media, herein referred to as the "surge loss" period. It is shown that water-loss data can be plotted so as to disclose the existence of a surge period, a non-uni-form cake thickness period, and a constant pressure filtration period. The same periods occur during exposure of consolidated porous media to muds. The data on consolidated porous media indicate that: (1) mud particles bridge pores inside porous media during the surge period, and (2) "filter cake" build-up inside porous media occurs during subsequent filtration. The data also show that the surge loss increases with sample permeability and with pressure differential. INTRODUCTION The phenomenon of mud filtrate invasion into porous sands of a drilling well has been recognized for many years.1,2,3,4 Part of API Code 29 is concerned with the filtration testing of a drilling mud to yield data on this subject. In a number of investigations "plastering properties" of muds were studied,5,6,7,8 "plastering" apparently meaning cake forming properties. In such studies the characteristics (thickness, permeability, and toughness) of the cake and the rate at which the liquid phase of the mud was separated from the solids (filtration rate through the cake, commonly referred to as water loss) were measured or at least considered. From the standpoint of its effect on well productivity, filtrate invasion into "clean" water-wet pay sands (i.e., those containing no clay minerals) may not necessarily be a serious problem. An increase in water saturation in the zone immediately around the wellbore would cause loss of oil permeability. However, in such a system, much of this water may be removed by oil production. If filtration occurs into "dirty" sands (i.e., those containing appreciable clay minerals), clay swelling or other mechanisms may cause losses in oil permeability which cannot be overcome by oil production.&apos;.&apos; The phenomenon of mud particle invasion into the pay sand of a drilling well was considered to be a possible serious factor in the early days of rotary drilling. Opinions varied as to whether drilling fluids "mudded up" and "sealed" oil sands. In 1932 Rubel,9 Gill,10 and Parsons," in separate papers, presented differences of opinion together with some laboratory and field data concerning loss of oil production caused by drilling fluid invasion into pay zones. These papers, and the discussions, furnish a large background on this subject and indicate the very clear thinking of many men at a time when petroleum production technology was in its infancy. Jones and Babson,6 and Silent,&apos; experimentally found that the depth to which mud particles invaded water-saturated sand packs was small (no greater than 1/16 in). Arn-quist12 in 1937 observed loss of water permeability due to invasion of mud particles into water-saturated, consolidated, sandstone samples. Williams and Cannon5 studied the filtra-tion properties of drilling muds and mentioned "sludge" which penetrated a short distance into the water-saturated filtering medium (sand pack). Byck5 concluded that formation permeability had no effect on the plas-

Jan 1, 1958

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 J. F. Smith

ELASTIC constants of yttrium and eleven of the rare earth elements have been measured. This has been accomplished by measuring the propagation velocities of ultrasonic pulses. The velocity measurements were made by noting the elapsed time between an applied pulse and the appearance of successive echoes. The pulse-echo technique has become relatively common, and the basis of the measurement is outlined in several standard tests, e.g., Heuter and Bolt.1 Two important assumptions are made when using this method for the determination of elastic moduli. First, the pulse is assumed to propagate as a plane wave. To justify this assumption, the cross section of the test specimen should be large compared to the wave length of the transmitted pulse. For these measurements on the rare earth elements the minimum cross section wave length ratio was about 20. A second assumption which must be made when using polycrystalline specimens is that the grains are sufficiently numerous and randomly oriented so that the specimen may be approximated as elasti-cally isotopic. The grain size in the as-cast specimens which were used is believed to be sufficiently fine for this approximation, and the degree of preferred orientation is believed to be small. Supporting this viewpoint is the fact that elasticity measurements by the pulse-echo technique on as-cast specimens of other metals give results which are in satisfactory agreement with values obtained by other techniques. Hence, it is believed that the measured elasticity values for the rare earth elements are not apt to be seriously in error due to the assumption of elastic isotopy. The apparatus used in this determination was a modified Sperry Reflectoscope with a precisely calibrated time base circuit. Piezoelectric transducers were used both to generate the pulse and to detect the echoes. X-cut quartz crystals were used for the longitudinal modes, and Y-cut quartz crystals were used for the shear modes. Frequencies of 2.25 and 5 megacycles per sec were employed. Most of the specimens were 2.5 to 5.0 cm in length. Results Table I is a tabulation of the measured propagation velocities of longitudinal waves and of shear waves, together with densities obtained by Sped- ding, Daane, and Herrmann2 from lattice parameter measurements. The shear modulus, Poisson&apos;s ratio, and Young&apos;s modulus were calculated from the data in Table I through use of the following relationships: µ = pv32 [1] s=2-(vb/vs)2/2[1-(vb/vs)2] [2] and Y= 2µ(l+s) [3] where s is the shear modulus, Y is the Young&apos;s modulus, s is Poisson&apos;s ratio, p is the density, V0 is the longitudinal wave velocity, and v, is the shear wave velocity. The calculated quantities are shown in Table 11. Compressibility values can be computed from the relationship and the computed values may be compared with measured values obtained by Bridgman.8 Table III lists the data for such a comparison. The agreement is satisfactory, being particularly good for neodymi- um and gadolinium, poor for samarium, and intermediate for the other elements. Some variation is expected since Bridgman&apos;s measurements are isothermal, whereas the present measurements are adiabatic. In addition there may be some effect due to small variations in purity. Though most of the rare earth metals measured by Bridgman and all of the metals used in the present measurements were prepared at this laboratory, minor purity variations might exist since the samples came from different lots. Also, any imperfections such as dislocations, vacancies, voids, grain boundaries, microcracks, etc., should contribute to the volume change of a com-

Jan 1, 1958

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 A. J. Opinsky

ThE superior performance of nonsag tungsten wire in lamps has been ascribed to the large-grained micro-structure that can be developed in it. The orientations of these large grains have been studied several times; most published data1-&apos; appear to be similar to those plotted in Fig. 1. These new data were obtained by X-ray back-reflection Laue technique from all of the large grains occurring in thirteen different wires that had been heated at the lowest possible temperature for the formation of large grains. Here the wire axis is plotted in terms of the principal directions of the cube. Rosi decided that the preferred orientation of the large crystals could be described by a single ideal orientation, (531), being parallel to the wire axis.&apos; Rieck2,3 and Mannerkoski&apos; have essentially confirmed this finding. Opinsky, Orehotsky, and Seigle argued that the data suggest that (211) is parallel to the wire axis instead of a single ideal orientation.5 This {211} contains the (531) ideal orientation and would appear to be a more general case. Ahlborn and Wassermann report that their orientation data stretch from ( 110) through (531) to (311) 8 This is part of the locus of (211). All these investigators have determined the orientations of the large grains by back-reflection Laue techniques. They have all obtained essentially similar results. On the other hand, Swalin and Geisler, who obtained their data by neutron diffraction, indicated that the preferred orientation of the large grains in doped wire is (110) .7 These findings cannot presently be reconciled with the pole density data described in the previous paragraph. Rosi1 and Rieck2 have advanced arguments about how their orientations could occur. Nevertheless, the crystallographic link between the (110) (cold-worked) fiber texture and the preferred orientation of the large grains has remained missing. This link can be provided through the concept of coincidence-type boundaries. Such boundaries separate two grains that have a certain number of common lattice sites. Coincidence relationships that result from rotations about low index directions are given by Brandon et a1 .&apos; What is desired is a calculation of those orientations that bear a coincidence relationship with the (110) fibers of the cold-worked matrix. This situation arises in the following fashion. Heating the tungsten wire for a combination of time and temperature falling short of the formation of the nonsag structure yields a structure that is still fibrous in nature and the preferred orientation remains (110). During grain growth, the growing grain is in contact with these fibers. It is hence possible that the entire process may begin by the passage of a coincidence boundary into a (110) fiber. The calculations were carried out analytically and checked graphically. Following Brandon et a1.,8 coincidence relationships from 1 in 5 to 1 in 19 have been considered. The results of the calculations are given in Fig. 2. Of the coincidences examined, some of those occurring upon rotation about ( 110) come closest to the experimental points in Fig. 1. Nineteen of the twenty-three data points in Fig. 1 can be attributed to the ideal orientations A, B, C, and D in Fig. 2. As determined analytically, three crystals lie within 4 deg of point A, four lie within 21/2 deg of point B, eleven lie within 5 deg of point C, and one lies within 1 deg of point D-a total of nineteen. The off-lying points are near the |110| point of the triangle.

Jan 1, 1968

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 E. J. Rapperport, M. F. Smith

A presentation of the W-Ru constitution diagram is given. Techniques utilized in the determination of phase boundary values include electron micro-probe analysis of two-phased alloys and diffusion couples, as well as normal metallographic and X-ray methods. The primary features of the diagram are: 1) a terminal solid solution of ruthenium in tungsten with a maximum solubility of 23 at. pct Ru at 2300°C; 2) a terminal solid solution of tungsten in ruthenium with a maximum solubility of 48 at. pct W at 2205°C; 3) a o phase of maximum breadth about 6 at. pct based on the composition W3Ru2 which forms peritectically from the melt at 2300°C, and which decomposes eutectoidally at 1667 °C to form a twigs ten and 0 ruthenium; 4) a eutectic at 45 at. pct Ru and 2205°C with the products being o plus ß ruthenium. THE W-Ru diagram has previously been studied only in a cursory fashion. Raub and alter&apos; obtained a 1400°C isotherm in which they observed no intermediate phases, and on which they established the limits of solubility as 36.5 at. pct W in ruthenium and about 1.5 at. pct Ru in tungsten. In addition, Obrowski2 found a o phase forming peritectically from the melt and existing only above 1650°C. Below this temperature the phase was presumed to decompose eutectoidally. The present work finds the diagram as given in Fig. 1. I) EXPERIMENTAL PROCEDURE The materials used for alloy preparation in determining the W-Ru constitution diagram were 99.9 pct pure ruthenium powder supplied by Baker Chemical Co., and 99.9 pct pure tungsten powder from General Electric Co. Typical analyses of these elements are given in Table I. Initial alloys at 10 at. pct intervals were prepared from the metal powders by the following method. Powders sufficient for 25 g of the alloys were weighed out with an accuracy of 0.1 mg and blended mechanically. After blending, the powders were compacted, in a steel die, at approximately 30,000 psi. The compacts were sintered in an electric vacuum furnace in order to remove adsorbed gases and to achieve partial densification prior to arc-melting. Vacua of 10-4 mm Hg or less were maintained in sintering as the furnace temperature was raised to approximately 2000°C. Sintering times ranged from 10 to 20 hr. The sintered compacts were arc-melted under a protective atmosphere of purified helium. Melting was conducted on a water-cooled copper hearth, utilizing a nonconsumable tungsten electrode. In the melting process, each alloy was turned over and re-melted on opposite sides from four to six times to ensure complete melting and to eliminate gross in-homogeneities. The arc-melter used had a vacuum capability of 5 X 10-6 mm Hg, and a leak rate of about 20 -liters per hr. Chemical analysis techniques for refractory metal-platinum group metal combinations are not well-established; therefore, composition control and determination depended principally upon weight-loss observations and calculations. This consisted in weighing each alloy after sintering and after arc-melting, and calculating the maximum and minimum composition values, assuming the total weight losses to be first all tungsten, and then all ruthenium. Since composition uncertainty was directly related to weight loss, care was taken to minimize losses in handling, compacting, and melting. Prior to homogenization and equilibration the as-arc-melted alloys were analyzed in several

Jan 1, 1964

By John W. Wagner, Robert K. Willardson

Single crystals of Pbl-xSnXTe have been grown from The melt under liquid B2O3 using the Czochralski technique. The PbTe-SnTe crystals were grown from near-stoichiometric melts and from melts with slight deviations from sloichiometry. Crystal growth rates ranging from 1 mm per hr to 1 cm per hr were employed, the latter being generally used. Several investigations were performed to characterize the single crystals grown In this study. The phase diagram of the PbTe-SnTe system was examined. X-ray analyses verified the single-crystal character of the crystals, and powder pattern lattice parameter determinations showed that Vegard&apos;s law was followed within the limits of the experimental error. The as-grown crystals were p-type with apparent carrier concentrations of -8 x 1018 to -8 x 1020 carriers per cu cm. Hall coefficients, resistivities, and carrier mobilities were determined as a function of composition. Dislocations were revealed by an electrolytic etch, and the crystals were found typically to contain 2 to 4 x 105 dislocations per sq cm. Microhardness measurements were performed; no maximum in the Vickers hardness us composition curve was seen. Mass spectrometry was used for impurity analyses, and the crystals were found to contain 1 to 2 x 1017 total p-type impurities per cubic centimeter. Distribution coefficients were calculated for the major impurities which were Na, Mg, Al, Si, Cl, and Zn. RECENTLY interest has been stimulated in the preparation and characterization of many alloys of the binary compound semiconductors. This interest is due primarily to the almost unlimited possibilities of adjusting the semiconducting characteristics of these materials by varying the alloy compositions. One alloy system which has been receiving extensive investigation is the PbTe-SnTe system, since these alloys show promise of being useful as emitters and detectors of electromagnetic radiation in the spectral range of 8 to 14 µ. This paper reports on the growth of PbTe-SnTe single crystals by the Czochralski technique and investigations of the general properties of these crystals. The phase diagram of the PbTe-SnTe system was investigated so that specific alloy compositions could be attained. I) CRYSTAL GROWTH The PbTe-SnTe single crystals were pulled from the melt using the Czochralski technique. Generally, the crystals were grown from near-stoichiometric melts, although special growth runs were made from both lead-rich and tellurium-rich melts. Growth of single crystals from up to 5 pct lead-rich melts presented no problems; however, melts with tellurium in excess of -1 pct caused volatilization problems which generally made crystal growth impossible. All melts were prepared from high-purity materials as follows: 1) lead— 6 N— Cominco (Cominco Products, Inc., Spokane, Wash.); 2) tin—5N—Cominco; and 3) tellurium— 5N+— American Smelting & Refining Co., Plainfield, N.J. No further purification of materials was undertaken in this study. The elements were reacted at -1000°C in a vacuum-sealed silica tube for a few hours, a gentle rocking action being used to ensure thorough reaction. The cast ingots were then transferred to a silica crucible for crystal growth. A schematic diagram of the growth apparatus is shown in Fig. 1. The Vycor tube is sealed at both ends by O-ring flanges so that a vacuum or a positive pressure may be maintained in the growth chamber. The pull rod and crucible may be rotated; all crystals produced in this study were grown with the crucible sta-

Jan 1, 1969

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 Raymond B. Ladoo

Wollastonite is a calcium metasilicate, with the formula CaSiO3; containing theoretically 48.3 pct CaO and 51.7 pct Si02. It is one of many natural and synthetic silicates with varying CaO/SiO2 ratios, with and without water of crystallization. While it is a very common mineral, deposits of sufficient size and purity to be of commercial interest are unusual. There is only one producer (1958) of wollastonite for industrial use in the United States, Godfrey L. Cabot, Inc. at Willsboro, New York. There has been a small production of surface material for ornamental use from near Blythe, California. Carload tests have been made on California wollastonite for making mineral wool and a commercial plant for this purpose was projected in 1957. Properties Wollastonite is monoclinic and commonly occurs in masses or aggregates of bladed or needle-like crystals. It has a perfect cleavage parallel to the long prismatic axis. It is rather brittle and some types grind easily to a very finely fibrous product, but other types, due to interlacing of fibers, are tough and difficult to grind. Mobs hardness is 4.5 to 5; specific gravity 2.8-2.9; index of refraction 1.616 to 1.631; melting point 1,512°C. Color when pure is a brilliant white, but when less pure it may be gray or brown. Luster is vitreous, transparent to translucent. Common mineral associates are garnet (several varieties), diopside, calcite and quartz. The nature of the mineral impurities determines to a large degree the commercial value of a deposit. At Willsboro, New York, the impurities consist chiefly of iron garnet and iron diopside which are both magnetic and so are easily removable by magnetic separation, yielding a nearly theoretically pure product. Some deposits in California contain calcite and quartz which cannot be removed cheaply, thus limiting market possibilities. Occurrence Wollastonite is a contact metamorphic mineral occurring in most places within or associated with impure limestones. The deposits at Willsboro, New York1,2,3,5 consist of two or more beds dipping 15-50°E and striking NW-SE. The main bed, 30 to 70 ft thick, may be traced on the surface for at least 2 ½ miles. In this belt, the Pre-Cambrian Grenville limestone has been injected and partially replaced by the more liquid portions of an anorthositic magma. Buddington and Whitcomb3 have described the rock as "Mixed gneisses, pyroxenite and garnetiferous gneisses and skarns." Prospecting revealed the wollastonite at ten different places in the belt, overlain in most places by a garnet rock. Diamond drilling has proven several million tons with probable reserves around 15 million tons. Interbedded with the wollastonite are beds of garnet from a few inches to several feet in thickness. In the wollastonite ore itself the chief and almost only associated minerals are garnet (mostly almandite but some andradite and grossularite) with small amounts of green hedenbergite. Inasmuch as the almandite and diopside are magnetic they are easily separated from the wollastonite in high intensity magnetic separators. If grossularite should occur in quantity other means of separation would be needed. Wollastonite has been reported at 35 localities in California12 but only those in the Big Maria and Little Maria Mountains, 16 to 20 miles north of Blythe, Riverside County, are

Jan 1, 1960

By T. C. Russell

The Conda phosphate mine, eight miles north of Soda Springs in Caribou County, Idaho, was opened up by the Anaconda Copper Mining CO. in 1920. Except for brief periods, during the 20&apos;s and early 30&apos;s, the mine has maintained a continuous production, and 2,100,000 short tons of phosphate rock have been shipped to the company&apos;s phosphate fertilizer manufacturing plant at Anaconda, Mont., or to independent processing plants on the Pacific Coast; a small tonnage of the rock has been shipped to the Hawaiian Islands. The Phosphoria formation on the Conda property consists of two, commercial-grade phosphate beds separated by 147 ft of black to brownish colored phosphatic calcareous shales interbedded with softer mudstones, clays, and occasional narrow seams of oolitic phosphate. The main lower phosphate bed in the series averaging 7.1 ft in thickness, is called the "foot-wall bed," which lies coriformably on the Wells limestone formation, the 1atter often containing irregular bands of chert. The upper or " hanging-wall bed" of phosphate rock averaging 7.2 ft in thickness, is overlaid by thick quartzite beds, locally called the " Rex chert" member in the upper portion of the Phosphoria formation. (Fig 1.) There are two anticlines on the property with axis striking approximately parallel to the mountain range beneath which extensive development on phosphate rock has been conducted in the past, and is now in progress. The phosphate beds have been eroded to a large extent from the tops of these anticlines, leaving at least three well-pronounced outcrops of the phosphate beds exposed within the boundaries of the Anaconda Copper Mining Cornpany&apos;s properties. At present, mining operations in the Conda No. 3 mine are confined to the two phosphate beds along the east flank of the easternmost anticline, where the dips on the beds vary from 50° to 60° east, thereby affording favorable conditions for the sublevel mining system now in use. Mining operations formerly were confined to the footwall or lower oolitic phosphate bed because of its higher phosphate and vanadium contents (32 pct P²O5 and 0.29 pct V2 O 5); this bed averages 7.1 ft in thickness. The oolitic portions of the upper bed were of satisfactory grade, but the shale and clay partings (Fig 2) diluted the mined rock and could not he separated economically by selective mining or by sorting. Experiments in beneficiating this rock were carried on for a number of years. Recently, a simple washing process was adopted, which gave a satisfactory grade of concentrates and a high recovery of P² O5. In 1947 it was decided to expand Anaconda&apos;s production of treble superphosphate and phosphoric acid by approximately 90 pct. This rock will be obtained from the footwall and hanging-wall beds, and the rock from the hanging-wall bed will be benefici-ated at -Anaconda.l In order to take advantage of the previous development on the 500 secondary haulage level, short crosscuts will be driven at approximately 950 ft intervals from the existing lateral drifts through the hanging-wall shale beds. From the inner end of each crosscut, short lateral drifts will he driven in both directions, so that four working raises can he put up on the dip of the phosphate bed at proper intervals along each of the lateral drifts. The mining operation on the footwall bed at Conda

Jan 1, 1950

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. E. Coleman, D. Hardie, A. E. Wraith

A photoguaplric method of measuring crack velocities has been applied to an examilzation of- the effect of hydrogen on the impact properties of zirconium. Results indicate that the crack in hydrided zirconit travels at about 26 m per sec whereas that in the uacuum -annealed is dependent on the speed of the hammer. RECENT work on the effect of hydrogen on zirconium reveals that when hydrided zirconium is tested in slow bending the crack producing failure can be unstable. The mode of fracture seems to involve the crack linking up broken hydrides by a ductile mechanism in the zirconium matrix.2" In order to compare the fracture of zirconium with that of other metals which show unstable crack propagation, notably steel, the rate of the crack spread must be known. As the methods previously used for measuring crack growth are either unsuitable for the present work5-&apos;&apos; or very costly," a simple technique has been devised in which the maximum crack velocity is derived from a series of crack position-time measurements. EXPERIMENTAL PROCEDURE The experimental arrangement is shown schematically in Fig. 1. The flash unit12 was triggered when the Charpy hammer touched the specimen and the 6-psec flash of the lamp delayed by a preselected time interval in the range 100psec to 10 msec. The camera was left on open shutter during the test. From direct measurement on a calibrated photographic print, Fig. 2, the position of the crack and the specimen was found at a known time after impact and, from a series of such tests using an appropriate range of flash-delay times, the crack velocity was estimated. Preliminary experiments were carried out on mild steel above and below its transition temperature. Vacuum-annealed zirconium, and zirconium hydrided to 100 ppm H were then tested at 20" and 150°C. For comparison, Zr-2.6 pct Nb alloy (in the 0 + transformed /3 condition), vacuum-annealed or hydrided to 100 ppm H, was tested at 20 C. The chemical analyses of these materials are given in Table I. For the high-temperature tests a fine chromel-alumel thermocouple was spot-welded onto each specimen close to the notch. The test piece was heated up to 200°C to allow enough time for preparing the apparatus while the specimen cooled to the testing tem- perature. It was assumed that the specimen cooled uniformly. The accuracy of the flash-delay time was better than i2 pct i 5 psec. The crack length was taken as its maximum distance traveled normal to the length axis of the specimen. Errors in these measurements arise as a result of the uncertainty in the location of the crack tip and the difficulty in defining the exact position of the crack starting point. The latter was due to the bonding and large amounts of deformation at the hammer contact point, especially in the vacuum-annealed specimens tested at 150°C. The maximum error in the measurements was however estimated to be about 5 pct. DISCUSSION OF RESULTS From the trial experiments using mild steel above its transition temperature it can be seen from the plot of crack length against time after impact, Fig. 3. that a reasonable estimate of the maximum crack velocity at the surface of the specimen may be made. Other features of note are the initiation time before the crack is first seen and the slowing down period

Jan 1, 1967

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