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By Albert Phillips

As EARLY As 1824, Haidinger1 described crystals of native copper that were, according to Dana,2 "probably twinned parallel to the octahedral plane and normal to this axis." In 1837, Rose3 very clearly demonstrated that native copper crystals were commonly twinned on the octahedral plane. Lasaulx,4 in 1882, described polysynthetic octahedral twins and stated that enclosed twinning lamellae were observed. Even on crystals formed artificially by. electrolysis, twinning was observed as early as 1886, by Brown.5 Many other descriptions of twinning in native copper and in gold and silver are to be found in the literature, and in every case with which we are acquainted the twinning is conformable to the spinel law; i. e., the octahedral plane is both twinning and composition plane. Metallurgists have long been familiar with the straight-sided bars or bands that commonly occur within the irregularly outlined grains of metallic crystalline aggregates. They are certainly found in nearly all metals of the face-centered cubic type after cold working and annealing. If a specimen showing these bands is rotated, keeping the angle of incidence of the illuminating beam constant, they usually exchange color contrast periodically with their respective matrix crystals. Also slip lines, when produced in these specimens, nearly always show a change in direction upon passing through the bands, giving rise to the "stairway" effect often illustrated in metallurgical textbooks. Apparently the only quantitative observations on bands of this sort were made by Osmond and Cartaud6 on austenitic steel. They selected,

Jan 1, 1928

By H. O. Jahns, R. A. Greenkorn, R. E. Haring, L. K. Shallenbarger

This paper is a study of the effects of heterogeneity on flow in an analog of porous media, the Hele-Shaw model. l-3 A set of experiments in heterogeneous Hele-Shaw models showed streamlines through and around heterogeneities of various sizes, shapes and levels. (A level, we define as the ratio between the transmissibility of the heterogeneity and that of the rest of the model.) The heterogeneities were restrictions or expansions of the flow stream analogous to variations in the transmissibility of porous media. The experimental data agreed well with numerical results and with an analytical solution, which we derived for a circular heterogeneity in an infinite field. This study considers the flow-stream distortion due to the shape, size and level of heterogeneities. Size and level are much more important than shape provided the heterogeneity is not long and narrow. Our analytical solution shows that a circular heterogeneity in a large field can be replaced by an equivalent circle of either zero or infinite permeability. The radius of the. equivalent circle is a simple function of size and level of the actual circle. INTRODUCTION With the availability of high-speed computers and numerical procedures to predict reservoir behavior, we are faced with an important question. How much information about the reservoir do we need to justify the cost of the computer in any given case? To answer this question, we have to know how various reservoir parameters affect flow behavior. Reservoir heterogeneity is one of these parameters. In this study, we used a simple, two-dimensional model of porous media, the hele-shaw model, to investigate the effect of heterogeneity on flow behavior. We restricted ourselves to linear, single-phase, steady-state flow in a rectangular field with a single heterogeneity at its center. The analogy between flow in Hele-Shaw models and in porous media is easily verified. Let us first consider a homogeneous Hele-Shaw model with constant plate separation h. (The Hele-Shaw model is constructed by placing two plates, usually glass, very close together and allowing liquid to flow between them. Streamlines are made visible by introducing colored fluid into the space between the plates at a number of points across the model.) We assume a cartesian coordinate system with its origin in the middle between the plates and the z axis directed perpendicular to the glass plates (Fig. 1). The fluid flow is always in a direction parallel to the glass plates and varies from a maximum value to zero in the very small distance from the middle (z = 0) to either plate (z = h/2). For slow motion of an incompressible fluid, neglecting inertia and body forces, we have the viscous flow equation: where p is the fluid pressure, p the viscosity, and v the velocity vector with components u, v and w in the x, y and z directions, respectively. In our rase. and the derivatives of 3 with respect to x and y are small as compared with the derivative in the z direction. Therefore, approximately, with Vp and v being two-dimensional vectors in the x-y plane. Two integrations with respect to z give

Jan 1, 1965

By M. E. de Morton

Recovery and early recrystallization of heavily deformed, 99.98 pct Cr was investigated by studying metallographic structure. X-ray line sharpening, electrical resistivity, plastic properties, internal friction, and shear modulus. Appreciable recovery of resistivity, internal friction, and shear modulus together with some hardening and relief of internal strains occurred before the visible growth of a textured substructure above 350°C (recrystallization in situ). The complex behavior of shear modulus, internal friction, and its strain amplitude dependence during annealing are discussed qualitatively in terms of the relative mobility of dislocations. BY plastically deforming fully recrystallized 99.98 pct Cr above the brittle to ductile transition temperature, at -350°C. as in wire drawing, chromium can be made very ductile at room temperature. However, this ductility is lost on annealing at high temperatures when recrystallization takes place.' The present investigation was made to determine the general pattern of the changes in a number of physical and mechanical properties during recovery and recrystallization of heavily deformed chromium as part of an effort to elucidate the reasons for lack of ductility in the fully recrystallized condition. PREPARATION OF MATERIAL Wire specimens 0.027 in. in diam were prepared from arc-melted, electrolytic chromium by extruding, hot swaging and finally wire drawing at 300" to 350°C, i.e. above the brittle-to-ductile transition temperature. The total reduction in area of the wire was 98 pct and the last 3 pct of reduction was made at 100" to 150°C before cooling to room temperature. The impurity content of the material is shown in Table I. Internal friction and modulus measurements were made on a single specimen after annealing in situ at successively higher temperatures. For all other measurements, a fresh specimen was used for each temperature and annealing of these specimens was done in evacuated (0.001 mm Hg) and sealed silica tubes for 1 hr at the various temperatures up to 700°C. EXPERIMENTAL METHODS AND RESULTS The occurrence of a. transition in some physical properties of chromium at - 40°C2 imposed limitations on the temperature region where some of the measurements could be made. The reason for this transition in chromium is at present unknown but is probably associated with an antiferromagnetic state observed below - 40°C.* Heavy deformation produces an anomalous decrease in resistivity when measured at temperatures below -40°C4 though a normal increase is observed above this temperature. On the other hand internal friction in heavily deformed chromium5 over the temperature range 40" to 50°C is invariant with temperature. Above and below this range internal friction is strongly temperature dependent, increasing with increasing temperature. A temperature in this range was therefore convenient for both resistivity and internal friction measurements and for consistency the measurements of the mechanical properties were also made at about this temperature. No structural change has, however, been observed in careful X-ray measurements6 between -195" and 50°C, i.e. departure from cubic symmetry was not greater than 3:10,000; X-ray line sharpening measurements were therefore more conveniently made at room temperature.

Jan 1, 1962

By Walter Rose, W. A. Bruce

Improved apparatus, methods, and experimental techniques for determining the capillary pressure-saturation relation are described in detail. In this connection a new multi-core procedure has been developed which simplifies the experimental work in the study of relatively homogeneous reservoirs. The basic theory concerning the Leverett capillary pressure function has been extended and has been given some practical application. Some discussion is presented to indicate the relationship of relative permeability to capillary pressure, and to provide a new description of capillary pressure phenomena by introducing the concept of the psi function. INTRODUCTION For the purposes of this paper the capillary character of a porous medium will be defined to express the basic properties of the system, which produce observed results of fluid behavior. These basic properties may be classified in the following manner, according to their relationship to: (a) The geometrical configuration of the interstitial spaces. This involves consideration of the packing of the particles, producing points of grain contact, and variations in pore size distribution. The packing itself is often modified by the secondary processes of mineralization which introduces factors of cementation, and of solution action which causes alteration of pore structure. (b) The physical and chemical nature of the interstitial surfaces. This involves consideration of the presence of interstitial clay coatings, the existence of non-uniform wetting surfaces; or, more generally, a consideration of the tendency towards variable interaction between the interstitial surfaces and the fluid phases saturating the interstitial spaces. (c) The physical and chemical properties of the fluid phases in contact with the interstitial surfaces. This involves consideration of the factors of surface, interfacial and adhesion tensions; contact angles; viscosity; density difference between immiscible fluid phases; and other fluid properties. Fine grained, granular, porous materials such as found in petroleum reser~oir rock possess characteristics which are expressible by (1) permeability, (2) porosity, and (3) the capillary pressure-saturation behavior of immiscible fluids in this medium. These three measurable macroscopic properties depend upon the microscopic properties enumerated above in a manner which defines the capillary character. Systems of capillary tubes or regularly packed spheres may be thought of as ideal and numerous references can be cited in which exact mathematical formulations are developed to show the relationships governing the static distribution and dynamic motion of fluids in their interstitial spaces. The capillary character of non-ideal porous systems such as reservoir rock also is basic in determining the behavior of fluids contained therein; although, in general, the connection is not mathematically derivable but must be approached through indirect experimental measurement. This paper gives consideration to the evaluation of petroleum reservoir rock capillary character. The methods employed may be applied to the solution of problems in other fields, and the conclusions reached should contribute to the basic capillary theory of any porous system containing fluid phases. In this paper, a modification of the core analysis method of capillary pressure is employed and it is intended to show that the capillary character of reservoir rock can be expressed in terms of experimental quantities. A very general method of interpretation correlating the capillary pressure tests with fundamental characteristics such as rock texture, surface areas, permeability, occasionally clay content and cementation is introduced. Eventually an attempt is made for establishing a method of deriving relative permeability to the wetting phase from capillary pressure data. The experimental evaluation of capillary character must be approached in a statistical manner if reservoir properties are to be inferred from data on small cores. This is implied by the heterogeneous character of most petroleum reservoirs, and suggests that considerable intelligence should be applied in core sampling. Finally, this paper supports the view that once the capillary character of a given type of reservoir rock has been established by core analysis, fluid behavior can then be inferred in other similar rock. Although no great progress has been made in establishing what variation can be tolerated without altering the basic fluid behavior properties, evidence will be presented to indicate that certain reservoir formations are sufficiently homogenous with respect to capillary character that the data obtained on one core will be useful in predicting the properties of other cores of similar origin. Tests have shown that cores under consideration can vary widely with respect to porosity and permeability and still be considered similar in capillary character. EXPERIMENTAL METHODS AND TECHNIQUES Various types of displacement cell apparatus for capillary pressure experiments have been described in the literature. Bruce and Welge; Thornton and Marshall; McCullough, Albaugh and Jones3; Hassler and Brunner; Lever-

Jan 1, 1949

By Walter Rose, W. A. Bruce

Improved apparatus, methods, and experimental techniques for determining the capillary pressure-saturation relation are described in detail. In this connection a new multi-core procedure has been developed which simplifies the experimental work in the study of relatively homogeneous reservoirs. The basic theory concerning the Leverett capillary pressure function has been extended and has been given some practical application. Some discussion is presented to indicate the relationship of relative permeability to capillary pressure, and to provide a new description of capillary pressure phenomena by introducing the concept of the psi function. INTRODUCTION For the purposes of this paper the capillary character of a porous medium will be defined to express the basic properties of the system, which produce observed results of fluid behavior. These basic properties may be classified in the following manner, according to their relationship to: (a) The geometrical configuration of the interstitial spaces. This involves consideration of the packing of the particles, producing points of grain contact, and variations in pore size distribution. The packing itself is often modified by the secondary processes of mineralization which introduces factors of cementation, and of solution action which causes alteration of pore structure. (b) The physical and chemical nature of the interstitial surfaces. This involves consideration of the presence of interstitial clay coatings, the existence of non-uniform wetting surfaces; or, more generally, a consideration of the tendency towards variable interaction between the interstitial surfaces and the fluid phases saturating the interstitial spaces. (c) The physical and chemical properties of the fluid phases in contact with the interstitial surfaces. This involves consideration of the factors of surface, interfacial and adhesion tensions; contact angles; viscosity; density difference between immiscible fluid phases; and other fluid properties. Fine grained, granular, porous materials such as found in petroleum reser~oir rock possess characteristics which are expressible by (1) permeability, (2) porosity, and (3) the capillary pressure-saturation behavior of immiscible fluids in this medium. These three measurable macroscopic properties depend upon the microscopic properties enumerated above in a manner which defines the capillary character. Systems of capillary tubes or regularly packed spheres may be thought of as ideal and numerous references can be cited in which exact mathematical formulations are developed to show the relationships governing the static distribution and dynamic motion of fluids in their interstitial spaces. The capillary character of non-ideal porous systems such as reservoir rock also is basic in determining the behavior of fluids contained therein; although, in general, the connection is not mathematically derivable but must be approached through indirect experimental measurement. This paper gives consideration to the evaluation of petroleum reservoir rock capillary character. The methods employed may be applied to the solution of problems in other fields, and the conclusions reached should contribute to the basic capillary theory of any porous system containing fluid phases. In this paper, a modification of the core analysis method of capillary pressure is employed and it is intended to show that the capillary character of reservoir rock can be expressed in terms of experimental quantities. A very general method of interpretation correlating the capillary pressure tests with fundamental characteristics such as rock texture, surface areas, permeability, occasionally clay content and cementation is introduced. Eventually an attempt is made for establishing a method of deriving relative permeability to the wetting phase from capillary pressure data. The experimental evaluation of capillary character must be approached in a statistical manner if reservoir properties are to be inferred from data on small cores. This is implied by the heterogeneous character of most petroleum reservoirs, and suggests that considerable intelligence should be applied in core sampling. Finally, this paper supports the view that once the capillary character of a given type of reservoir rock has been established by core analysis, fluid behavior can then be inferred in other similar rock. Although no great progress has been made in establishing what variation can be tolerated without altering the basic fluid behavior properties, evidence will be presented to indicate that certain reservoir formations are sufficiently homogenous with respect to capillary character that the data obtained on one core will be useful in predicting the properties of other cores of similar origin. Tests have shown that cores under consideration can vary widely with respect to porosity and permeability and still be considered similar in capillary character. EXPERIMENTAL METHODS AND TECHNIQUES Various types of displacement cell apparatus for capillary pressure experiments have been described in the literature. Bruce and Welge; Thornton and Marshall; McCullough, Albaugh and Jones3; Hassler and Brunner; Lever-

Jan 1, 1949

By Richard L. Stowe

Four NX-diameter holes were diamond-drilled in competent granite. Samples of the recovered core were used in laboratory tests. A borehole, plate-bearing device known as a Goodman jack was used to perform load deformation tests on the rock in the core hole. The majority of samples used in the laboratory tests were taken from depths in the hole at or within 5 ft of those at which the plate bearing tests were made. Borehole camera records, compressional and shear wave velocities, and densities were measured. Dynamic elastic constants were computed for the in-situ material, while comparative data (except camera records) were obtained in the laboratory. These data were examined to evaluate the significance of the in-situ modulus of deformation (Ed), the value computed from Goodman jack tests. Average test results show an excellent correlation between in-situ and laboratory data. The ratio of laboratory to field deformation modulus ranges from 9.82 to 7.21 for 3,000 and 9,000-psi stress levels, respectively. The dynamic modulus ratio, ED field/Ep lab, is 1.02; the compressional wave velocity ratio, V8 field/V8 lab, is 0.94; the shear wave velocity ratio, V, field/V, lab, is 1.12; and the density ratio, field [y/y] lab, is 0.95.

Jan 1, 1973

By C. H. Mathewson

BeRyllium, magnesium, zinc and cadmium, together with mercury, constitute a coherent sub-group of the periodic system and these metals, excepting mercury, have been studied in sufficient detail by the new X-ray diffraction methods to prove their common adherence to the hexagonal close-packed type of crystal structure with a progressive increase in axial ratio as we pass through the group from beryllium to cadmium. The first four columns of Table 1 summarize the data on crystal structure of these metals reported in the International Critical Tables.' The last two columns are based on results obtained in the present investigation. Twinning has often been observed in zinc and cadmium. The general aspects of this twinning are abundantly illustrated by photomicrographs, diagrams, etc., in the papers by Romig, and Mathewson and Phillips reported to this Institute in 1927.2 A determination of the composition

By H. W. Straley

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

Jan 1, 1946

By H. W. Straley

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

Jan 1, 1946

By Herman Garlichs

THE development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately, $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870: Lead production in South-west Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 ,tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a V. Wood and galena were placed in the furnace and ignited. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 ft. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required, for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 7, 1917

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell' It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully's theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By D. O. Hobson, P. L. Rittenhouse

We have recently found that many lots of Zircaloy-2 and -4 tubing tested in tension deform to cross section shapes that are "polyhedral" rather than circular. The noncircular cross sections seem to result from a circumferential variation in plastic proper -ties and, therefore, in texture. We examined the diffracted X-ray intensity from (OOOl), {1010), {ll20}, and {1011} planes parallel to the tubing surface around the entire circumference. Tubing that deformed to a circular cross section showed <5 pct variation in diffraction intensity around the circumference from any of these planes. Greater intensity variations were found for all the tubing materials that developed non-circular cross sections during deformation. In each instance the number of intensity maxima and minima was consistent with the number of sides of the &apos;polyhedral" cross section. THE effects of crystallographic texture on the mechanical properties of zirconium, zirconium alloys, and other anisotropic hexagonal materials such as titanium and hafnium have been intensively studied. If the natural crystallographic anisotropy of these materials could be controlled by selected fabrication operations, a material could be produced with a texture, or preferred orientation, in which the maximum strength directions are in the stress directions of the structure. The permissible stress levels of the structure could then be increased. Rittenhouse and Pickle-simerl have shown that highly textured Zircaloy-2 plate can vary from 52,000 to 70,000 psi in tensile yield and from 62,700 to 122,000 psi in compressive yield strengths as a function of specimen orientation. Similar texture effects have been observed in Zircaloy tubing, whose mechanical properties differ depending upon whether the tubing has basal poles predominantly radial or tangential and upon the mode of testing. These same texture effects might be troublesome if the texture in the tubing is not uniform around the tube walls. This paper is concerned with the effects of nonuniform texture on the strain behavior of commercial Zircaloy tubing. BACKGROUND Previously, various lots of commercial Zircaloy tubing were tested under selected stress conditions as part of a program to determine the four quadrants of the yield locus. One of the testing procedures was uniaxial tension and it is the influence of texture variations on the tensile deformation behavior of the tubing that is of interest here. The effect of texture on the strain behavior in tubing is very apparent from a uni-axial tensile test.2 This behavior is illustrated schematically in Fig. 1 for three different tubing textures: 1) basal poles predominantly in the radial direction; 2) basal poles predominantly in the tangential direction, and 3) basal poles equally distributed between the radial and tangential directions. In the first example most of the grains are oriented for prism slip to operate to allow axial lengthening and diametral reduction of the tube. Reduction in wall thickness requires {1122} twinning, a more difficult operation than slip.* In the second example, the texture is such that *The singleCrystal analogy will be used quite often in this paper when strong texturesare being discussed. The textured material is assumed to react as if it were a single crystal aligned in the same orientation and under the same stress system as the predominant texture._____________________________________________ prism slip operates to give axial lengthening and wall thinning. Diametral reduction requires twinning and again should be more difficult to accomplish. A specimen with basal poles equally distributed between the radial and tangential directions should exhibit about equal diametral and wall strains.* Table I shows the *Diametral strain is accomplished by a combination of circumferential and longitudinal strains. But, for the purposes of this paper, it will be considered as a strain causing a change in the length of a specified diameter.__________ strain behavior of two lots of tubing with different textures. The first tube has a texture with basal poles equally distributed between the radial and the tangential directions. The ratio of true thickness strain to true diametral strain is almost unity. The second tube has a predominantly radial basal pole texture and it is apparent that most of the total strain has occurred by diameter reduction, just as one would predict. There is over three times as much diametral strain as thickness strain. RESULTS We found that specimens from certain lots of commercially fabricated tubing did not retain round cross sections during uniaxial testing. Instead, the speci-

Jan 1, 1970

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4&apos;6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

By David R. Poirier

Activity data of carbon as a function of both temperature and composition throughout the stable austenite range is correlated by mearts of an equation derived from a quasi-chemical model. The carbon activity data of austmite for temperatures between 800° and 1200°C are utilized in conjunction with the activity of carbon calculated for the y solidus using the activity of carbon in liquid iron and published austenite-liquid equilibria. The results agree very well with Chip-man&apos;s correlation; however, a small difference in the activity of carbon in the high-temperature range of the austenite field is evident. Excellent agreement is found for the heat of solution of graphite in infinitely dilute austenite; from this study the value is 10,550 cal as compared with Chipman&apos;s value of 10,680 cal. AS part of a program to study microsegregation in dendritic solidification of ternary Fe-C-Cr alloys, it was desirable to be able to describe the equilibria between austenite and liquid iron in Fe-C-Cr alloys. In this regard, it was necessary to correlate existing data on the activity of carbon in Fe-C austenite as a function of both temperature and composition. At that time, Chipman&apos;s analysis1 of the thermodynamics of binary Fe-C austenite was not available. It will be shown that this study and Chipman&apos;s study agree rather well throughout the stable austenite range of temperature and composition; however, some small differences appear at temperatures greater than the eutectic temperature. Benz and Elliott 2 presented isoactivity lines for austenite superimposed on their revised Fe-C phase diagram. Using an expression from Darken and Gury 3 representing Smith&apos;s4 activity data between 800" and 1000°C, they found that the activities extrapolated above 1000°C to the solidus did not agree with the activities determined from the corresponding liquidus compositions. It is the purpose of the following argument to reconcile carbon activity data of austenite with the activity in liquid Fe-C alloys as determined by Rist and Chipman. 5 In addition, a simple analytical expression is sought for computational convenience. ACTIVITY DATA OF CARBON IN ZRON Fig. 1 shows the activity of carbon in Fe-C austenite as determined by Smith, 4 Schenck and Kaiser, 6 Scheil et a1.,7 and Bungardt et al.&apos; The lines are merely drawn to separate the data into the respective isotherms. These data are inadequate to determine the activity of carbon at temperatures greater than 1200°C. The activity coefficient in Fe-C liquid alloys was assumed by Rist and chipmans to obey the following

Jan 1, 1969

By C. E. Shoenfelt, D. E. Winchester

NO important discoveries of petroleum during 1933 were reported from New Mexico. Lea and Eddy counties were the centers of activity during the drilling season and each had a number of interesting completions. The Hobbs pool, in Lea County, was definitely outlined on the east, north and northwest. Under an agreement reached last summer by state officials and operators, the Hobbs pool was continued under proration throughout the year. One hundred eighty-four units of 40 acres each were being produced at the end of 1933. The allowable was 21,306 bbl. daily at the beginning of 1933, but when the agreement was revised in the spring the minimum was raised to 30,000 bbl., and by the end of the year had been raised to 33,473 bbl. At present the field is being prorated on the basis of 25 per cent on acreage and 75 per cent on potentials except in the southwestern edge of the field, where water encroachment is a problem. In this area the basis of proration is 40 per cent on acreage and 60 per cent on potentials. A corrective method employed in this part of the field has been partly successful. The water is advancing in the upper part of the pay, a dolomitic limestone, and in a number of instances packers have been set in the pay below the water and above the oil. The locating of a satisfactory seat for a packer is difficult and in some instances has not been a complete success. Pipe line runs from the field during the year aggregated 11,413,218 bbl., bringing the total gross production up to 41,093,681 bbl., of which 39,000,-000 bbl. has been produced under proration, which went into effect on July 10, 1930. On Nov. 30, potentials were determined on the assigned pressure basis and the total was reduced 71,165 bbl. daily, to 1,265,-332 barrels. The outstanding completions in the Hobbs pool were three in number, of which the best was the Humble Oil & Refining Company&apos;s No. 3B Bowers in sec. 20, 18S., 38E., with an initial production of 11,664 bbl. of oil and 10,000,000 cu. ft. of gas. The Shell Petroleum Company&apos;s No. 4B McKinley, in the same section, produced at the rate of 22,940 bbl. of oil while flowing open, but when tubed, flowed at the rate of 6610 bbl. The third outstanding well, No. 4 Hardin of the Tidal Oil Co., and located in

Jan 1, 1934

By Paul Billingsley

THE mining districts of the first and second order1 of the western United States (and borders) are those named on Fig. 1. These fall into four groups: (1) in the eastern outliers of the Rocky Mountain system; (2) in the Rocky Mountain system itself; (3) in the Great Basin; and (4) in the Sierras and Coast ranges. Of these four groups, the first three are almost entirely of Tertiary age and are within a belt of Tertiary compres-sive folding which we shall call the Rocky Mountain-Great Basin thrust arc. The backbone of this belt is shown by the line BAC. The position of the ore districts in this belt indicates a conformance to linear elements of the continental pattern. These are additional to the peripheral elements emphasized by Butler.2 NATURE OF THE THRUST ARC The thrust arc separates regions of contrasted kinds. To the east of it are flat-lying plateaus interrupted by earlier mountain folds; to the west, sunken basins, in which block-faulted ranges lie like an anchored fleet in a sea of desert wash or lava. The cross-sections are as shown in Fig. 2.

Jan 1, 1933

By T. M. Allen, W. H. White

THE Greenwood-Grand Forks area of southern central British Columbia, known as the Boundary District, has a long history of mining exploration and production. At the turn of the century this was the premier copper mining camp in the British Empire, its total production amounting to some 20 mil- lion tons. Most of this ore came from the great Granby mines at Phoenix, but the Motherlode mine at Deadwood camp, 6 miles to the west, and several mines in Summit camp, 5 miles north of Phoenix, made important contributions. The large deposits were exhausted in 1918 and the district since has seen only desultory exploration and salvage operations. The orebodies are mineralized skarn zones in limestone members of a thick series of Upper Paleozoic sedimentary and volcanic strata. Chalcopyrite is the primary ore-mineral. Copper carbonates and silicates occur sparingly in outcrops, but the oxidized zone generally is very shallow. Much of the surface is mantled by glacial drift which in most places ranges in thickness from 2 to 15 ft. In some of the hanging valleys, however, the glacial drift may be as much as 100 ft thick and may assume drumlin-like forms.

Jan 1, 1954

By N. Mungan

Laboratory imbibition and displacement experiments were performed using crude oil and cores drilled with water and preserved under anaerobic conditions. The purpose of these tests was to determine reservoir rock wettability and to find out if more oil could be recovered by use of NaOH solution than by conventional waterflooding. The preserved cores were found to be oil-wet. Contrary to work in the literature, these cores changed to water-wet upon contact with air. After exposure to air for a week, the cores yielded more oil by waterflooding than when preserved under exclusion of air. At reservoir temperature of 160F, flooding the preserved cores with 0.5N NaOH solution recovered more oil than an ordinary wa-terflood, and additional oil when following a waterflood. When the caustic solution was used from the beginning, all the extra oil was obtained before breakthrough; when the caustic followed a conventional waterflood, the extra oil was produced in the form of an oil bank ahead of the injected caustic. The increase in oil recovery resulted from wettability reversal. Also, use of caustic reduced the volume of injection required to flood out the cores. At room temperature, however, the caustic solution did not reverse the wettability and gave no additional oil recovery. Cores which had become water-wet by air exposure or caustic flooding were restored to their original oil-wet state when saturated with crude oil and allowed to equcilibrate at reservoir temperature for two weeks. Therefore, in the absence of preserved cores, it may be possible to restore weathered cores to their original wettability for use in laboratory floods. INTRODUCTION Waterflooding has been in use since 1865, and is by far the simplest of secondary recovery methods. Unfortunately, most waterfloods are inefficient in recovering oil, often leaving half or more of the original oil in place un-recovered. The low oil recovery generally results from low sweep efficiency and low displacement efficiency. Consequently, to increase oil recovery by waterflooding, sweep and displacement efficiencies should be improved. Sweep efficiency is primarily affected by reservoir heterogeneities and mobility ratio, while displacement efficiency is affected by the capillary forces between fluids and rock surfaces. For petroleum reservoirs, the capillary forces are expressed in terms of interfacial tension and wettability. If oil recovery is to be improved significantly in water- flooding, the capillary forces holding the oil in the raervoir porous matrix must be reduced or eliminated. One way to reduce capillary forces is to inject commercial surfactants ahead of the injection water into the reservoir. Laboratory tests of this method have shown no promise of an economical process yet, and no increase in oil recovery was obtained in the field trials which have been reported. Work is continuing in many companies to find surface-active agents which, in workable concentrations, can yield substantial added oil recovery. Another way to change capillary forces operating in petroleum reservoirs is by changing the pH of the injected water. Wagner et al.&apos; showed that change in the pH sometimes activates the surface-active materials natural to some crudes and brings about gross wettability change. Since pH alteration can be obtained with cheap chemicals, such as hydrochloric acid or sodium hydroxide, the process shows promise of being economical in a field application. Pan American Oil Corp. reported oil recovery by use of caustic solution from a flooded-out reservoir.&apos; Their test, conducted at a small additional cost, yielded results which were so sufficiently favorable and encouraging that the wettability reversal flood was expanded to portions of the field not previously flooded.13 It is important to bear in mind that changes in the pH of the water not only can reverse wettability but also can lower the interfacial tension between water and crude oil. Reisberg and Doscher4 have studied the pH dependency of the interfacial tension of Venture crude using sodium hydroxide solutions of various concentrations. Their data show that the interfacial tension was lowered from 23.0 to 0.02 dynes/cm by increasing the NaOH concentration from 0.005 to 0.5 per cent by weight. Thus, the use of NaOH may lead to additional oil recovery due to both wettability reversal and lowering of interfacial tension. Whether alteration of pH results in wettability reversal from oil-wet to water-wet and increases oil recovery depends on wetting properties of the reservoir rock and the crude. This necessitates delicate laboratory experiments, with suitable core and fluid samples from a field. Although many investigators have studied wettability reversal floods in the laboratory,1,2,5,6 these studies have been carried out with synthetic porous media, refined laboratory fluids and surface-active chemicals to simulate the process. The study presented in this paper is the first time that wettability reversal by pH alteration has been accomolished in laboratory core floods using carefully preserved natural cores, live crude and with experiments performed at reservoir pressure and temperature.

Jan 1, 1967

By Herbert H. Uhlig

A STUDY of passivity in chromium-iron alloys holds considerable interest, both because of the present-day practical importance of the stainless steels, and because of the scientific importance attached to the mechanism of their corrosion resistance. Upon the discovery of the passive chromium-iron alloys in 1912, it seemed logical to attribute the observed phenomenal corrosion resistance to a thin, continuous, protective reaction product on the surface. The product was thought to be Cr2O3 or a similar oxide containing both chromium and iron. This mechanism seemed likely in view of Michael Faraday&apos;s conjecture that passive iron is not reactive in concentrated nitric acid because of an oxide on the metal surface.† Since 1912, data have accumulated that permit a further exploration into the nature of passivity and provide a new approach to the problem. A summary of the facts lends considerable weight to a mechanism based not on physical protection of an oxide or similar compound, although such compounds may be present on the surface, but to a change in tendency of surface metal atoms to react chemically. This change in reaction tendency is ascribed to chemisorbed films that effectively satisfy residual valence forces of the metal surface, but do not appreciably disturb the positions of metal atoms in the lattice. In other words, formation of a new lattice such as that of an oxide is not a necessary condition for this type of passivity. The decreased reaction tendency of the metal by reason of chemisorbed films can thereby account for low reaction rates of the stainless steels in many media, as well as a noble galvanic potential as is observed. Substances capable of adsorbing on the stainless steels, and hence accompanying the property of passivity, are typically oxygen, nitrites or chromates, but are not in any sense limited to these. Other elements and compounds can also chemisorb, and therefore may also play a major part in the mechanism of passivity in specific media. The mechanism of passivity based on chemisorption or activated adsorption begins with the interpretation Langmuir proposed for his experiments concerning adsorbed oxygen on tungsten.1 He found that adsorbed oxygen was tightly bound, remaining on the tungsten surface above temperatures at which WO3 rapidly volatilizes. The oxygen in such a state did not readily react with hydrogen even at

Jan 1, 1947

Discussion of the paper of E. C. HARDER, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 94, October, 1914, pp. 2573 to 2586. I. C. WHITE, Morgantown, W. Va.-I have seen some of the great iron-ore deposits described in this paper. -One of these in the State of Minas Geraes appears to be an immense mountain of iron ore about 2,000 ft. in height. All over its surface from bottom to top may be seen large masses of rich iron ore, varying in weight from a few pounds to several tons, and from all that one can judge without exploitation, the quantity of available ore is certainly very large in this particular mountain. Whether it will prove a mere surface deposit or shell, like the famous Iron Mountain of Missouri, is for future exploration to determine. The question of transportation is the main factor in determining the availability for exportation of these Brazilian iron ores. There is no coal in Brazil that can be manufactured into coke without expensive previous treatment, since the best of the raw coal in the States of Rio Grande do Sul, Santa Catharina, and Parana, contains about 35 per cent. of ash, of which about 6 per cent. is sulphur, and coal of this composition cannot be utilized in iron smelting without purification. When I was chief of the Brazilian Coal Commission in 1904 to 1906, I had a cargo of this coal shipped to Balk, Germany, and treated in the great coal-testing plant of the Humboldt Engineering Works, located just across the Rhine from Cologne. It was found that by crushing and washing the Brazilian coal, it yielded 33 per cent. of briquetting coal, containing only 10 to 12 per cent. of ash (of which 1 per cent. was sulphur), and 42 per cent. of slack coal, with 25 per cent. of ash and low in sulphur, so that about 33 per cent. of the Brazilian coal could be converted into coke of fair quality, as shown by the following average of three analyses, using air-dried coal, of briquets made from the Barro Branco coal bed, State of Santa Catharina: Moisture 1.56 Volatile matter 31.66 Fixed carbon 56.73 Ash : 10.05 Total 100.00 Sulphur 1.34 Phosphorus 0.003 B.t.u 13,395

Jan 4, 1915