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By S. R. Maloof, W. R. Mitchell, J. A. Mullendore

Preliminary experimental evidence is presented to show that the metallic impurities aluminum, iron, and silicon, and beryllium oxide as found in commercially pure hot-pressed beryllium powder can be reduced to lower Concentrations by Zone -Purification techniques. The reduction in the concentration of aluminum to extremely low levels (10 PPm) is noteworthy, since earlier work demonstrated that aluminum is a major factor contributing to the hot-tearing of beryllium during fusion welding. On the basis of present findings, a method is suggested for producing beryllium metal of improved weldability. EXPERIMENTAL research now being conducted on the purification of beryllium indicates that several of the metallic impurities and beryllium oxide can be reduced to lower concentrations by employing standard horizontal zone-refining techniques. For the preliminary work, commercially-pure hot-pressed beryllium having a purity of 97.84 pct was used. The chemical composition is given in Table I. The hot-pressed beryllium was machined into bars 5/8 by 5/8 by 4 to 6 in. in length. Beryllium-oxide boats which had been conditioned by prior heating in a vacuum of 10"5 mm of Hg at 1100°C for 3 hr were used to hold the beryllium while it was zone melted. The boat with its charge, along with a smaller beryllium-oxide boat containing scrap beryllium to be used for gettering purposes, was loaded into a quartz tube and evacuated to 10-6 mm of Hg. Alter alternately evacuating and flushing three times with purified argon, the furnace tube was backfilled to a pressure of 1/6 atm of A and sealed off by means of a vacuum-tight stopcock. It was then removed from the pumping equipment and mounted on the traveling carriage of the zone-refining apparatus. Heating was accomplished with a 10 kw 450 kc induc- tion heating unit using an induction coil consisting of two turns of 3/16-in. diam copper tubing. Before starting to zone melt, the atmosphere in the furnace tube was gettered by heating the scrap beryllium in the smaller boat to above its melting point and holding at temperature for several minutes. The carriage was then shifted so as to locate one end of the beryllium ingot in the large boat within the induction coil. A molten zone approximately 3/4 to 1 in. was established by loading directly into the ingot. The molten zone was moved very slowly along the length of the ingot. Before each pass was made the procedure for evacuating, flushing, and backfilling, and so forth was repeatedI' Speeds of 1 1/2 and 3 in- per hr were used with up to twelve zone passes. The appearance of a typical zone-refined ingot is shown in Fig. 1. After zone refining, the grains in the ingot appear to be elongated in the direction of zone travel, whilst before, they are essentially equi-axed. A microexamination revealed the presence of a network in the beryllium grains as seen in Fig. 2. Laue spots in back reflection pictures taken of the sample were not sharp, indicating the presence of subgrains in the structure. As can be seen, however, many of the network boundaries cross beryllium grain boundaries. It has been shown by Martin and Moore1 that beryllium solidifies as a bcc structure which then transforms to the hexagonal structure at about 1250oC.It is believed that the observed network is merely the outline of the bcc structure which formed from the melt and are not subgrain boundaries. In order to eliminate surface contaminants, approximately 1/16 of an inch of material was removed from the outer skin of each ingot after zone refining.

Jan 1, 1962

By J. J. Gilman

RECENT experiments have shown that the mar-tensite reaction in a standard tool steel is influenced by the history of the reacting austenite. The martensite reaction proceeds to a given extent at a higher temperature in austenite formed from an annealed spheroidal structure than it does in austenite formed from tempered martensite: that is to say, a prequench lowers the temperature range of the martensite reaction in this steel. Furthermore, a prequench alters the appearance of the martensite as compared to martensite formed from "virgin" austenite. The steel used for this work was a manganese nondeforming tool steel of the following composition: C, 0.85 pct; Mn, 1.43; Si, 0.23; Ni, 0.12; Cr, 0.59; and W, 0.59. A piece from a rolled bar was forged to Vz in. sq and annealed to a spheroidal structure. Disks 1/8 in. thick were used in the experiments. Several sets of the specimens were prepared and austenitized in lead at 1475°F. Three sets were held at 1475°F for 15 min, quenched in water, and immediately reheated to 1475°F. After this quench the three sets were held for 5 min, 30 min, and 3 hr, respectively, at 1475°F and then the individual specimens in each set were quenched in molten baths to 325", 300°, and 275ºF, respectively, and held for 15 sec. Immediately after the quenching treatments? the specimens were tempered at 600°F for 30 sec to darken the martensite and then were quenched in water. The holding times were short enough to avoid isothermal transformation. Three other sets of specimens were given the same final quenching treatments as the first three, but they were austenitized at 1475°F for 20 min, 35 min, and 3 hr and 15 min, respectively, without an intermediate water quench. The two individual specimens from each set were quenched together in order to eliminate quenching errors. Several experiments were run in this way but only the six sets referred to are described in detail because they all yielded essentially the same results. By means of the stated heat treatments the martensite reaction was investigated for: 1—austenite formed from an annealed structure, and 2— austenite formed from tempered martensite. The martensite reactions of the two types of austenite differed significantly. This is shown by Figs. 1 and 2. Comparison of the photographs on the left in Figs. 1 and 2 with those on the right shows that less martensite was formed by a quench to a given temperature from prequenched austenite than from austenite formed from an annealed structure, that is, the prequench suppressed the martensite reaction. The effect was observed for specimens austenitized 20 min, 35 min, and 3 hr and 15 min. A comparison of Figs. 1 and 2 shows that the martensite reactions in both sets of specimens occurred at lower temperatures with increased austenitization time. This was caused by the increased dissolution of residual carbides with time at 1475°F. However, the difference in amount of martensite formed in prequenched austenite as compared to virgin austenite was approximately the same for all three austenitization times. One further observation should be noted. The needles of the martensite formed from virgin austenite are somewhat longer on the average and show less of a tendency to cluster than those of martensite formed from prequenched austenite. This causes the martensite on the right in Figs. 1 and 2 to have a more acicular appearance than the martensite on the left. Since the sets of specimens used in this work were austenitized for identical total lengths of time and the effect of a prequench on the martensite reaction existed for specimens held at the austenitizing tem-

Jan 1, 1953

By O. J. C. Runnals

The intermetallic compounds NpAl2, NpAl3, and NpAl have been prepared, and examined by X-ray diffraction methods. The compounds are isostructural with the corresponding U-Al compounds. NpAl3 is face-centered cubic with a = 7.785A and has the MgCu2 structure. NpAl is simple cubic with a = 4.2624 and has the AuCU3 structure. NpAl4 is body-centered orthorhombic with a = 4.428, b = 6.268, and c = 13.71A. The published description for the atomic positions in UAl, applies also to NpAl4 THE U-Al system has been examined by Gordon and Kaufmann.1 They identified the following intermetallic compounds: UAI2, UAl3, and a third, tentatively identified as UAl5. A structure analysis of the latter compound by Borie2 proved that the formula UAl4 was more consistent with the X-ray data. The crystal structures of UAl2 and UA have been reported by Rundle and Wilson.3 UAl2 was found to be isostructural with MgCu. The atomic positions in the simple cubic UA1, cell were found similar to those in the AuCu3 structure. Three analogous compounds exist in the binary system Np-Al. X-ray data for the compounds NpAl2, NpAl3, and NpAl4 are reported below. The neptunium used in the investigation was supplied through the courtesy of the Argonne National Laboratory as neptunium (V) nitrate. It was stated to have a radioactive content of 99.25 pct Np237. The impurity limits had been established by a spectrographic analysis given in Table I. Any titanium, boron, or bismuth impurity should be effectively removed during the fluorination of NpO2 to NpF4, and sodium, lithium, magnesium or strontium during the alloying procedure. The oxalate ignition technique, described by Westrum for the preparation of finely-divided reactive PuO2, was used.The neptunium (V) nitrate solution, containing 100 mg Np, was evaporated to dryness on oxalic acid crystals. The resulting oxalate was calcined to NpO, by heating in platinum at 650°C for 2 hr. An equimolar mixture of anhydrous hydrogen fluoride and purified hydrogen was passed over the NpO2 for 2 hr at 500°C. According to Fried and Davidson" the above fluorination conditions should produce the purple-black fluoride, NpF3 However, the light-green product showed only NpF4 lines on an X-ray diffraction pattern and contained only an estimated 5 pct of finely dispersed black NpF3 particles on microscopic examination. NpAl3: An intimate mixture of 50 mg of neptunium fluoride and aluminum powder (99.99 pct pure, —28 to $60 mesh) was heated to 900°C in a BeO crucible in vacuum by a tungsten coil for 2 hr, to allow the following reaction to proceed: NPF4 + 7Al + NpAl, + 4AlF. [1] The formation and sublimation of aluminum mono-fluoride in this system was verified from an X-ray diffraction analysis of the sublimate. The diffraction pattern was similar to one obtained in the aluminum reduction of UF4 to UF3,6 showing both Al and AlF3 lines. The resulting alloy was sintered at 1100°C for 1 hr. A powdered specimen of the crystalline product was sealed in a thin-walled quartz capillary for X-ray examination. The photograph was taken on a 14.32 cm General Electric powder diffraction camera, using filtered copper radiation. The films were calibrated in terms of a NaCl standard pattern. The wavelengths used in the calculations were 1.5418A for Cu K and 1.5405A for Cu K The powder diffraction pattern showed that NpAl is simple cubic with a = 4.262 % 0.005A, and is isostructural with UA13 where a = 4.27A1 or a =

Jan 1, 1954

By J. Serra, M. Turpin, R. Alberny

A new method is proposed to obtain automatically an unbiased estimate of the interdendritic spacing A. It is shown that the structure can be built by a random distribution of a rectangular basic unit. The usual definition of the interdendritic spacing yields a value 1 which, coupled with A, gives the shape of the basic rectangular unit. A study of the relationship between dendrite arm spacing and solidification rate was conducted as a part of a research program on dendritic solidification. For any comparison between theory and experiments to be meaningful, it is necessary to measure reproducible and clearly defined spacings. Fig. 1 shows clearly that even in a fairly simple structure such measurements are difficult. if we compare photos (a) and (b), we can hardly assess which one shows the larger spacing. Moreover, the quantity to be measured can be defined in several ways. On a small scale, dendrites seem to be distributed in a very regular and ordered way. However, on a larger scale, this regularity no longer exists. The usual way to measure spacings is to pick up some rows of dendrite stalks; such measurements are obviously biased since less orderly regions are not taken into account. A more objective method is to section the picture with randomly oriented straight lines and average the measured interdendritic spacings. The purpose of this paper is to show that such measurements, which can be conducted automatically, yield objective and reproducible results which are directly related to characteristic features of the dendritic structure. I) THEORETICAL ANALYSIS 1-1) Mathematical Morphology and Function of Co-variance. Matheronl and Serra2 enlarced- the definition and geometrical meaning of the notion of covariance to encompass problems in mathematical morphology. A brief review of part of their theory can be stated as follows. Let A' be an isolated particle, and let us consider a group of two scanning points h is the vector joinlng these points, h its modulus, and a its direction. Let us also define a boolean function, k(x), whose value is 1 if x lies inside the particle and 0 if it 1s outside. The total number of events in which both points are inside A' IS the covariance Ii',(h): is the measure of the intersection of A' with the particle ALh obtained by translating A' of -h Obviously K,(O) is the volume of the particle A', or its area if A' is a two-dimensional body. The average value of K,(h), when the direction of a vector h of constant modulus is rotated, is: An important property of the covariance is illustrated on Fig. 2: if the shape of a particle shows some regularity along a direction a, K,(h) generally presents a maximum. We now consider a group A, made of many particles A' distributed in space; then k(x) is taken as the realization of a stationary random f~nction.~ The volume fraction (or fraction of area if the problem is two-dimensional) occupied by A equals the average value q of k(x): meaning "average value of"). We also replace

Jan 1, 1970

By C. S. Yust, J. W. Smith, J. R. Walsh, R. E. Simpson

This paper presents the results of a complete reservoir studv designed to determine a sound economic program for the conservation of oil and gas in the Pickton field, Hopkins County, Texas. The Pickton field produces from the Bacon Lime with all indications of the study being that production is predominately by dissolved-gas drive. Calculations of the total ultimate recovery to be expected under primary operations indicated only 16.7 per cent of the oil originally in place would be recovered. This unusually low recovery is due to the type of drive operating and the extremely high dissolved gas-oil ratio and shrinkage. Results are presented for six plans of returning gas to the reservoir, evaluated to determine (1) comparative recoveries and economics of (a) returning gas at a constant rate by supplementing Pickton gas with extraneous gas during the early portion of the operation, and (b) conventional gas-return operations without using extraneous gas, and (2) the optimum size of compressor plant for each type of pressure maintenance. The over-all economic program considers, for either type pressure maintenance operation. a gasoline plant to process the unusually rich casinghead gas. Since pressure maintenance will disturb equities, pooling of royalties is in the case of Pickton a prerequisite to conservation of oil by this type of operation, both from an economic and legal standpoint. In the event pooling of royalties cannot be achieved, the study considers a gasoline plant to operate under a modified primary production operation which will make the conservation of gas possible. INTRODUCTION The Pickton field, located in Hopkins County, Texas. was discovered in November, 1944. by the completion of Humble's C. D. Nichols 1, in the Bacon lime of the Lower Glen Rose formation, through perforations from 7,888 to 7.896 feet. The well initially produced 50.2 API gravity oil with a gas-oil ratio of 1,350 cubic feet per barrel. Subsurface samples of the reservoir fluid obtained soon after completion of the discovery well showed that the Pickton crude is unique in that it has an extremely high dissolved gas-oil ratio and is subject to very severe shrinkage. Calculations of the future behavior of the Pickton reservoir indicated that ultimate oil recovery by primary operations would be 3,269,000 barrels, representing only 16.7 per cent of the oil in place (19,577,000 stock-tank barrels), and that recovery could be substantially increased by returning the produced gas. The cumulative production of 1,382,694 barrels on November 1: 1947, amounted to 42.3 per cent of the estimated ultimate oil recovery from primary operations. The purpose of this study is to determine and evaluate the optimum program for conservation of oil and gas in the Pick-ton field, including the desirability of conducting gas-return operations and of installing a gasoline plant. LOCATION AND DESCRIPTION Pickton Field, The Pickton field, as shown in Fig. 1, is located in southwest Hopkins County, Texas, 12.5 miles southwest of the New Hope field, 2.7 miles northeast of the Coke field, 16 miles southwest of Sulphur Springs, and 8 miles northwest of Winnsboro, Texas.

Jan 1, 1949

By C. S. Yust, J. W. Smith, J. R. Walsh, R. E. Simpson

This paper presents the results of a complete reservoir studv designed to determine a sound economic program for the conservation of oil and gas in the Pickton field, Hopkins County, Texas. The Pickton field produces from the Bacon Lime with all indications of the study being that production is predominately by dissolved-gas drive. Calculations of the total ultimate recovery to be expected under primary operations indicated only 16.7 per cent of the oil originally in place would be recovered. This unusually low recovery is due to the type of drive operating and the extremely high dissolved gas-oil ratio and shrinkage. Results are presented for six plans of returning gas to the reservoir, evaluated to determine (1) comparative recoveries and economics of (a) returning gas at a constant rate by supplementing Pickton gas with extraneous gas during the early portion of the operation, and (b) conventional gas-return operations without using extraneous gas, and (2) the optimum size of compressor plant for each type of pressure maintenance. The over-all economic program considers, for either type pressure maintenance operation. a gasoline plant to process the unusually rich casinghead gas. Since pressure maintenance will disturb equities, pooling of royalties is in the case of Pickton a prerequisite to conservation of oil by this type of operation, both from an economic and legal standpoint. In the event pooling of royalties cannot be achieved, the study considers a gasoline plant to operate under a modified primary production operation which will make the conservation of gas possible. INTRODUCTION The Pickton field, located in Hopkins County, Texas. was discovered in November, 1944. by the completion of Humble's C. D. Nichols 1, in the Bacon lime of the Lower Glen Rose formation, through perforations from 7,888 to 7.896 feet. The well initially produced 50.2 API gravity oil with a gas-oil ratio of 1,350 cubic feet per barrel. Subsurface samples of the reservoir fluid obtained soon after completion of the discovery well showed that the Pickton crude is unique in that it has an extremely high dissolved gas-oil ratio and is subject to very severe shrinkage. Calculations of the future behavior of the Pickton reservoir indicated that ultimate oil recovery by primary operations would be 3,269,000 barrels, representing only 16.7 per cent of the oil in place (19,577,000 stock-tank barrels), and that recovery could be substantially increased by returning the produced gas. The cumulative production of 1,382,694 barrels on November 1: 1947, amounted to 42.3 per cent of the estimated ultimate oil recovery from primary operations. The purpose of this study is to determine and evaluate the optimum program for conservation of oil and gas in the Pick-ton field, including the desirability of conducting gas-return operations and of installing a gasoline plant. LOCATION AND DESCRIPTION Pickton Field, The Pickton field, as shown in Fig. 1, is located in southwest Hopkins County, Texas, 12.5 miles southwest of the New Hope field, 2.7 miles northeast of the Coke field, 16 miles southwest of Sulphur Springs, and 8 miles northwest of Winnsboro, Texas.

Jan 1, 1949

By F. H. Wilson, E. W. Palmer

The solid solubility of iron in 2 to 10 pct cupro-nickels increases with temperature and nickel content. Property changes accompanying various heat treatments indicate typical precipitation hardening behavior. Iron content also affects softening temperature and sub-scale formation. These factors, as well as impingement corrosion resistance, influence the optimum iron content of commercial alloys. FOR many years Cu-Ni alloys have been used extensively in the form of tubes, pipes, and plates for the construction of salt-water lines and surface condensers on shipboard and in tidewater power stations. The 30 pct Ni alloy has been considered more resistant to rapidly flowing sea water than alloys of lower nickel content, and has been standard on ships of the U. S. Navy. Some ten years ago, the still better corrosion resistance obtained by modifying the 30 pct Ni alloy with approximately 0.5 pct Fe was recognized, and the iron-bearing alloy rapidly superseded the plain alloy as the standard material for severe service. In 1945, Tracy and Hungerford1 published a study of the effect of iron on the corrosion of various cupro-nickels in sea-salt solutions, and their data indicated that the 10 pct Ni alloy containing about 0.75 pct Fe was equivalent to the 30 pct Ni alloy containing 0.5 pct Fe. This was confirmed by LaQue in discussion of the above paper, and by results in an experimental condenser set up at the Kure Beach marine test station of The International Nickel Co., reported by Freeman and Tracy.' The 10 pct Ni iron-bearing alloy is now being very widely used in applications where the 30 pct Ni iron-bearing alloy was formerly considered standard. While this "substitution" has undoubtedly been stimulated by the present extreme shortage of nickel, it must be emphasized that it involves no loss of service performance, and would have occurred anyway in the course of time, for economic reasons. In view of the increasing use of the 10 pct alloy, it seems desirable to make generally available the results of several investigations of Cu-Ni-Fe alloys carried out in the Metallurgical Research Laboratory of The American Brass Co. in recent years. The present paper, deals with the constitution of these alloys in the copper-rich corner of the system, and with the variations in hardness and tensile properties resulting from the heat treatment of alloys containing various amounts of iron. Most of this work is concerned with alloys containing 10 pct Ni. With over about 0.75 pct fe, the 10 pct Ni alloy is suscep- Alloys Several series of cupro-nickel alloys containing iron were used in these investigations. Most of them were prepared in the laboratory, but two samples of commercially fabricated alloys were included. Series A—Nominally 2 and 5 pct Ni, each with 0 to 1.5 pct Fe. Series B—Nominally 10 pct Ni with 0.1 to 0.4 pct Fe. Series C—Nominally 1.0 pct Ni with 0 to 2 pct Fe. Series D—Nominally 10 pct Ni with 3 to 5 pct Fe. Series E—Nominally 10 pct Ni with 1 and 1.5 pct Fe.

Jan 1, 1953

By J. W. Martin, L. K. Singhal

Grain boundary M23CB precipitates have been shown to form by a process involving the migration of an austenite grain boundary, and each plate of precipitate is in parallel orientation with one of the austenite grains constituting the boundary. The carbide distribution and morphology appear to be sensitive to grain boundary mis orientation. Some areas of austenite grain bowzdary permit the development of an array of M,C, particles, some of which are in parallel orientation with one grain and some with the other grain constituting the boundary. Massive carbide at grain boundary triple points is also shown to be in parallel orientation with one constituent grain. PREFERENTIAL precipitation during aging of carbides of the type (Fe,Cr)23C6, usually written MZ3C6, in grain boundaries of quenched austenitic stainless steels has been widely recognized. M23C6 has a complex cubic crystal structure' which contains ninety-two metal atoms and twenty-four carbon atoms per unit cell. Less energy is involved in forming grain boundary precipitates than in the formation of intragranular precipitates, and the process is further enhanced by the accelerated diffusion rates in the boundaries and by the probability of segregation of chromium atoms and carbon atoms to the region of the grain boundaries during prior solution heat treatment in order to reduce lattice strain. Early electron micrographic studies2, 3 involving either extraction replica or normal replica techniques established the geometric or dendritic form of the carbide particles, although this approach led to dis- pute as to whether the particles grew within the plane of the boundary or grew into the matrix.4-6 More recent thin-foil studies' have claimed to identify a discontinuous precipitation process involving M23C6 at grain boundaries, and the object of the present work was to attempt to clarify the situation using modern electron micrographic and diffraction techniques. 1) EXPERIMENTAL 1.1) Material. The steel selected for this work had a base composition of 24 pct Ni-25 pct Cr-3 pct Ti and contained about 0.04 pct C. The full analysis if given in Table I. This alloy was in the form of strip which had been hot- and cold-rolled to a thickness of 0.6 mm. 1.2) Heat Treatment. Specimens 4 cm long by 1 cm wide were solution-heat-treated for 3 hr in argon at 1150°C, followed by water-quenching. Specimens were subsequently aged in vacuo at 750°C for periods up to 500 hr. 1.3) Preparation of Electron Microscope Specimens. The heat-treated strips were cut bv spark machining into discs of 3 mm diam and 0.6 mm thickness. he-discs were dished on both sides using an electrolytic jet of 15 pct HCl electrolyte at 80 v. Final electro-polishing of the discs was carried out using 10 pct perchloric acid, 20 pct glycerol, and 70 pct ethanol at 10 v. The current density was kept below 300 ma. cm"2 by cooling the electrolyte to 0" to 5°C. As soon as a small hole appeared, the electropolishing was stopped and the specimen was quickly washed with ethanol.

Jan 1, 1969

By B. Paul

1. INTRODUCTION It is known that the elastic modulus of a metal may be considerably increased by dispersing

Jan 1, 1961

By E. H. Edwards, J. Washburn

Zinc crystals were deformed in simple shear and it was found that anisotropic strain hardening occurred in which the inactive slip systems were hardened more than the active system. The formation of dislocation barriers by dislocation interaction was discussed as a possible explanation of the hardening of the latent systems. STRAIN hardening which accompanies slip in a metal crystal is not limited to the slip systems actively contributing to the plastic strain. There is also a strengthening of the latent slip systems which are crystallographically equivalent to the active system. In the case of aluminum deformed in tension, Taylor and Elam1 found that plastic flow on one set of octahedral planes caused either the same or a slightly greater hardening on an inactive set. Similar results have been obtained for crystals of a brass2 and of Cu-A1 solid solutions.3 Experiments by Rohm and Kochendorfer4 indicated that the hardening of the active system exceeded the hardening of any latent system for aluminum crystals deformed in shear. On the other hand, strain hardening in zinc and cadmium crystals tested in simple shear at —196°C was recently found to be greater in the latent than in the active slip direction." When the strain direction was shifted during testing to a direction 60" from the original, a higher stress was required for glide to continue than would have been needed for flow to proceed in the original direction. The relation between the hardening of active and latent systems must be complex, depending upon the relative orientations of the systems and upon the experimental techniques used to deform the crystal. A detailed knowledge of the hardening produced in latent systems would be valuable in choosing between possible dislocation models of the strain-hardening process. The experimental data now available are incomplete and even contradictory. The present study was undertaken to provide quantitative information regarding the relative amount of hardening of active and latent systems for a particularly simple case. Zinc crystals were deformed in simple shear along one of the three crystallographically equivalent directions [250], [1210], and [1120] in the slip plane, and the relative hardening produced in each of these directions was compared. Experimental Procedure and Results The single crystals of 99.99 pct purity zinc used in this investigation were grown from the melt in the form of 1 in. diam spheres. Shear specimens were acid-machined from the crystals by a method which has been described previously. The gage section of the test specimen was a cylinder having a height of 1/8 in. and a cross-sectional area of approximately 1/3 sq in. All specimens were machined with the axis of this cylindrical gage section aligned with the [0001] axis of the crystal. An innovation in the design of the shearing apparatus for these tests was the provision for a rapid shift in the direction of the applied stress from one slip direction to any other slip direction lying in the same slip plane. Fig. 1 shows a section through the specimen and shearing apparatus, and Fig. 2 is a

Jan 1, 1955

By J. H. Smith, H. W. Paxton

ALTHOUGH many structural and kinetic investigations have been made for alloys of iron and nickel, only meager data exist from thermodynamic investigations. The purpose of this note is to estimate the free energy of the Fe-Ni solid solutions from thermodynamic data available for ternary alloys containing iron and nickel. The lack of a description of the thermodynamic behavior for the Fe-Ni system has required the structural and kinetic analyses of the system to assume some form of solution behavior, usually regular, e.g., the mar-tensite transformation analysis of Kaufman and Cohen, 1 consistent with the limited thermodynamic data. Indications that this system could exhibit ideal solution departures might have been suggested by the large deviations from additivity rules observed in the density and lattice-parameter measurements of Jette and Foote2 who interpreted this in terms of possible solute-solvent interactions. Later Turkdogan et al. 3 and more recently Ward and wright 4 found a minimum in the graphite solubility in liquid Fe-Ni solutions near the concentration of FeNi3 with deviations from linearity persisting at all concentrations. This was interpreted by Ward and wright4 to indicate negative heats of solution and was suggestive of short-range ordering. The infinitely dilute activity coefficient of carbon (?oC) was also observed by smith5 to pass through a maximum near the FeNi3 concentration in Fe-Ni solid solutions. Recent investigations of the liquid solutions over the entire concentration range by Zellars et a1.' and Speiser et a1.," using vapor-pressure determinations, revealed both negative departures from Raoult's law and a nonregular solution behavior. The solid alloys have been studied by Oriani 8 and Kubaschew-ski and von Goldbeck6 employing gaseous H2/H2O equilibria with Fe and FeO. Both investigations were in substantial agreement, indicating very small departures from ideality. However, Oriani observed the formation of Fe3O4 (instead of FeO) at XFe= 0.441 which severed the equilibrium and precluded experimental investigation of the nickel-rich alloys. Heat-capacity and heat-content measurements have been evaluated by Montgomery10 and found generally unsatisfactory for gleaning thermodynamic information. This is due to the unknown final states of the alloys caused by the interference of the martensite transformation on cooling iron-rich concentrations and superlattice formation, magnetic transformation, and the varied heat treatments used by investigators of nickel-rich concentrations. As an alternative to the experimental difficulties, indirect estimates of the solid-solution behavior have been made by Fleischer and Elliott11 and Smith et a1.12 From their measurements of the solubility of Fe-Ni alloys in liquid lead, Fleischer and Elliott calculated the nickel activity (aNi) (and integrated for aFe) by assuming: 1) liquid lead has no solubility in solid Fe-Ni alloys, 2) Henry's law is obeyed throughout the liquid lead-rich phase (0— 12 at. pct Nil, and 3) Henry's law constant is independent of relative iron and nickel concentrations. The estimate of Smith et a1.12 was obtained

Jan 1, 1964

By D. Havlena, A. S. Odeh

The use of the straight-line method of solving the material balance equation is illustrated by means of six field cases. Also, the application of statistical criteria to arrive at the most probable answer is shown. The theory underlying the straight-line method of solution and the applicability of the statistical criteria was presented in a previous paper.' The field cases include saturated and undersaturated oil reservoirs with and without water drive. The aquifers discussed are: limited radial, infinite radial, very small aquifer and infinite linear. The field cases also include a gas reservoir producing under water drive. INTRODUCTION In a previous paper,' the authors presented the theory underlying the solution of the material balance as an equation of a straight line. The appropriate equations for various material balance cases as well as the methods of analysis and interpretation with comments and discussion were also included. To illustrate the various theoretical cases treated previously, five field cases are analyzed in this paper by employing the straight-line method of solving the material balance equation (MBE) and one example previously published is referred to. The use of statistical criteria to arrive at the most probable answer is also shown. All the field examples presented, except Case 2, are excerpts from complete reservoir studies. To illustrate the method, only sections specifically dealing with the material balance principles are included. Additional geologic information and basic data are reported to better acquire an understanding of the cases and thus to better follow the reasoning that suggested the successful application of the straight-line method of solving the MBE. The six cases are: (1) saturated reservoir, small gas cap, limited aquifer; (2) saturated reservoir, very small gas cap, infinite aquifer; (3) undersaturated-saturated reservoir, very small aquifer; (4) highly undersaturated reservoir, no water drive; (5) high undersaturated one-well reservoir, limited aquifer; and (6) gas reservoir, infinite linear aquifer. THE D4 SAND, GUICO FIELD, VENEZUELA The D, sand, which was discovered in 1943, is presently in a depleted state. Since its discovery it has produced under water drive, gas-cap-gas expansion, and solution gas drive. In Nov., 1947, water injection was initiated to arrest further pressure decline. When discovered, the D, sand was a saturated reservoir with a gas cap /oil zone volume ratio m estimated volu-metrically at 0.0731, an average permeability of 500 md, a porosity value of 25 per cent, and an oil viscosity at reservoir conditions of 0.3 cp. The volumetrically determined stock-tank oil initially in place was 23.1 million bbl. The volumetrically weighted physical data and production data available until Nov., 1953 are reported in Table 1. In Ref. 1, the effects on the straight-line plot of various values of ro/r for a constant ?to, or of various dimen-sionless times for a constant r8/r10 were theorized and were illustrated in Fig. 3A of that reference. In this field case, the previously theoretically predicted effects are established. Thus, the MBE calculations using Eq. 3c of Ref. 1 were performed for various r6/r10 and dimension-less time values. Eq. 3c of Ref. 1 is:

Jan 1, 1965

By J. Murray Riddell

The method of treating hazards wherein value is decreased, is cited by R. D. Parks. Quite properly, the theory of probabilities is made use of when multiple hazards are under consideration. E. F. Fitzhugh, Jr. $ deals with the enhancement phase graphically and uses percentage of expectancy as derived by a study of conditions and the selection of a chance factor. It is believed that both of the authors referred to fully recognize the part which human judgment plays, and as coupled with experience, training, and the application of the theory of probabilities; in that respect the composer of this paper is in accord. Within the past year, the task of arriving at a mathematical method for handling the enhancement phase, and, additionally, coupling the negative and positive phases, was explored. In citing the hazard, or negative phase, reference is made to the text by Parks. Types of Items far Consideration On the hazard, or negative, side some of the common items to be considered are: 1. Subsidence and resulting damage. 2. Flo wage of water above that anticipated. 3. Geological. (a) Decline in quality of probable ore, and/or (b) Decline in quantity of probable ore. 4. Depressed economic conditions. 5. Litigation. Similarly, on the enhancement, or positive, side common items to be considered are: 1. Flo wage of water below that estimated. 2. Geological. (a) Increase in quality of probable ore, and/or (b) Increase in quantity of probable ore. 3. Elevated economic conditions. 4. Litigation. 5. Technological advance in the art. Tn all of the above items no consideration is given to placing a value on, or giving consideration to, possibilities. For example, referring to Table 1, the estimated normal present value (Vp) of a property, exclusive of risk consideration, is taken as $100,000. If subsidence affects the usefulness of the shaft, the present value of the property will decrease to $60,000, and it is judged that there is a 1 in 4 chance that the shaft will be impaired;, consequent.ly, if subsidence took place, the present value would be reduced ($100,000-$60,000) $40,000, but since the chance is 1 in 4, the allowable reduction would be only one-fourth of $40,000, or $10,000, or a discount of 10 pct (hazard factor) of the original value; the related safety factor is taken as unity minus 0.10, or 0.90. Thus, the original Vp, $100,000, multiplied by the safety factor ($100,000 X 0.90) gives $90,000, which is the adjusted present value of the property in this single instance. Additionally, there is a water hazard, which, if encountered, will reduce the present value to $85,000. The chance is 1 in 3. Following through with the same reasoning as shown above, the derived safety factor will be 0.95. To arrive at a single multiplying factor which will express the combined risks, the two safety factors are multiplied together, 0.90 X 0.95 = 0.855. That factor when multiplied by the origirial Vp will give the adjusted, and

Jan 1, 1950

By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

By H. C. Gatos, J. T. A. Pollock, V. Sadagopan

PREVIOUS investigations on the effect of neutron irradiation on the superconducting properties of bulk transition metals indicated that little or no change occurred in poly crystalline disordered materials, particularly if cold-worked prior to irradiation. Only the superconducting properties of ordered intermetal-lic A15 compounds were found to be sensitive to irradiation, and the observed reduction in Tc and increased magnetic hysteresis or critical current densities were attributed to the introduction of flux pinning vacancy clusters and disorder in the lattice. Since the former would also be expected to be present after irradiation in disordered alloys, the general conclusion was that the disordering effect of the irradiation was the primary reason for the changes observed. The present note reports some unusual effects of neutron irradiation on cold worked Nb(Cb)-Ti-V alloys. Specimens with nominal composition as given in Table I were prepared by repeated arc melting, taking the usual precautions, and homogenized at 1000°C for 24 hr prior to a reduction of 15:l by cold rolling. Samples of size 1 by 1 by 25 mm were sliced from the rolled strips. The sarmples chosen for irradiating were sealed in a cadmium tube (wall thickness 1 mm) prior to exposure in a fast neutron flux of 3.7 x 1019 neutrons per sq cm in the swimming pool reactor of Union Carbide Corporation&apos;s Sterling Forest Reactor. During irradiation the temperature of the samples was maintained below 70°C. The irradiated samples were stored at room temperature for approximately 1 year allowing the radiation levels to reach a safe handling value. Tc measurements were made employing a self-inductance coil technique. Jc data at 4.2"Kwere obtained using a four lead resistivity method. The latter measurements were made at the Francis Bitter National Magnet Laboratory by setting the perpendicularly applied field and increasing the direct current through the sample until a potential of about 10-6 v was detected. Tc values for the nonirradiated samples are listed in Table I together with the change in Tc after irradiation. A decrease in Tc of 0.25 or 0.3"K was measured for three of the four samples, the exception being the Nb-30 at. pct V-20 at. pct Ti alloy which showed a decrease of 0.5K. Jc vs applied field data are plotted in Fig. 1 for the Nb-20 at. pct V-30 at. pct Ti alloy. These curves are typical of the four alloys and surprisingly indicate that a degradation occurred in all the samples after irradiation. Hc2 values, obtained by extrapolation to zero current, are 8 to 15 pct lower than those measured for the nonirradiated specimens. The reasons for the degradation of Tc and jc ob-served in the alloys on exposure to neutron irradiation are not immediately apparent. The temperature at which the samples were maintained during bombardment (<70°C) and stored (20°C) make it highly unlikely that any significant change in the dislocation density of the materials through thermally activated migration and annihilation would occur. The explanation must lie in the type of damage produced by the bombardment. McEvoy et a1. reported no change in superconduct-

Jan 1, 1970

By Otto H. Henry, Edward L. Badwick

Up to the present time, according to Hansen1 and Haughton,2 the constitution of the bismuth-indium system has not yet been published. The generally accepted value for the melting point of indium, as listed in most scientific journals and textbooks, is 155°C. Recently, however, H. M. Davis3 has determined a new melting point for indium of 257.3°C ± 0.1°C. Since bismuth has been used in preponderance as an alloying element in the majority of low-melting alloys, and indium has been used with considerable success in lowering the melting points of low-melting alloys,4,5 an interest has been developed in the application of these two metals, making a complete knowledge of the constitution of its alloys desirable. In this investigation, the melting point of indium reported by H. M. Davis has been found to be substantially correct. A value of 157.2°C ± 0.5°C was determined. The two eutectic compositions have been placed at 34 and 50 pct bismuth with their respective eutectic temperatures as 72.4&apos;C ± 0.5°C and 90°C ± 0.5°C. The bismuth-indium phase diagram has been determined by thermal and microscopic analysis and is shown in Fig I. THERMAL ANALYSIS Granulated bismuth and indium shot, having a guaranteed purity of 99.99 and 99.95 pct, respectively, were melted in a carbon crucible by means of a laboratory heater. To minimize oxidation of the alloys, a heavy mineral oil (Nujol) having a high flash point was used. A platinum-platinum rhodium thermocouple 0f fine wire encased in a thin-walled Pyrex glass tube, about 1/8 in. in diameter, was connected to a type K potentiometer for temperature measurements. The thermo-couple was calibrated against the melting points of tin, bismuth, and the silver-copper eutectic and the boiling point of water. Since the temperature readings could be reproduced to 0.2°C, and the accuracy of the temperature standards in this range is slightly better than 0.5°C, it seems reasonable to assume that the temperature readings are reliable to approximately 0.5°C. The cooling rate could be controlled by varying the amount of insulation surrounding the crucible. Three or four layers of asbestos paper, 1/16r, in. thick, sufficed to give a cooling rate of from 1° to 2°C per minute. Undercooling was slightly noticeable. This condition was minimized by vigorous stirring, since the advantage of using slower rates was too small to justify the greater expenditure

Jan 1, 1947

By Maurice C. Fetzer, Charles R. Austin

It has long been known that plain high-carbon steels may be susceptible to graphiti-zation below the A1 critical, but no data have been available to indicate what factors cause and tend to inhibit graphite formation. Two recent publicationsl,2 have shown that the factors controlling graphitization below the A1 are different from those operating above the A1 inversion where commercial graphitization of malleable iron begins. Furthermore, for plain high-carbon steels graphitization below the critical point does not appear to be related to ordinary chemical analyses. Many years ago it was recorded3 that the rate of graphitization at subeutectoid temperature is not a maximum just below the A1 critical, but at some lower temperature, which Austin and Norris have shown to be about 670°C. Indeed, work done in our laboratory has demonstrated that it is impossible to spheroidize certain steels in the temperature range of 650° to 710°C. without the formation of considerable amounts of graphite. However, if the temperature is maintained just below the A1 (720°C.) these same steels may be completely sphe-roidized at constant temperature. In previous studiesl,2,4 on I per cent plain carbon steels graphitization was encountered during prolonged tempering. The limited number of steels studied did not provide sufficiellt data to permit adequate study of the factors controlling this graphitization. Accordingly, a limited statistical investigation was undertaken, utilizing 18 steels of similar chemical analyses, furnished by four steel companies, who also supplied information regarding the history of manufacture. An extensive program of research is being carried out on these steels, including the effect of pretreatment and atmosphere on the nature and extent of graphitization, and the possible correlation of graphitization with such characteristic properties as hardenability, grain size and mechanical behavior. In the present paper discussion is restricted to a study of the correlation between graphitizing tendency at 670°C. after quenching from several temperatures above the critical, and (I) the minor variations in the chemistry of these steels of "similar" chemical composition, and (2) the deoxida-tion practice employed. The state of the lead bath, oxidized or protected from oxidation by charcoal, used in the tempering treatments is also considered. Materials Eighteen plain carbon steels of about I per cent carbon, and containing similar amounts of each of the other common elements usually found as impurities, were obtained in the form of rods % in, in diameter from four steel manufacturers. The analyses for ordinary and special elements of all the steels were made on the rod stock as received in the laboratory, and the re-

Jan 1, 1941

By Maurice C. Fetzer, Charles R. Austin

It has long been known that plain high-carbon steels may be susceptible to graphiti-zation below the A1 critical, but no data have been available to indicate what factors cause and tend to inhibit graphite formation. Two recent publicationsl,2 have shown that the factors controlling graphitization below the A1 are different from those operating above the A1 inversion where commercial graphitization of malleable iron begins. Furthermore, for plain high-carbon steels graphitization below the critical point does not appear to be related to ordinary chemical analyses. Many years ago it was recorded3 that the rate of graphitization at subeutectoid temperature is not a maximum just below the A1 critical, but at some lower temperature, which Austin and Norris have shown to be about 670°C. Indeed, work done in our laboratory has demonstrated that it is impossible to spheroidize certain steels in the temperature range of 650° to 710°C. without the formation of considerable amounts of graphite. However, if the temperature is maintained just below the A1 (720°C.) these same steels may be completely sphe-roidized at constant temperature. In previous studiesl,2,4 on I per cent plain carbon steels graphitization was encountered during prolonged tempering. The limited number of steels studied did not provide sufficiellt data to permit adequate study of the factors controlling this graphitization. Accordingly, a limited statistical investigation was undertaken, utilizing 18 steels of similar chemical analyses, furnished by four steel companies, who also supplied information regarding the history of manufacture. An extensive program of research is being carried out on these steels, including the effect of pretreatment and atmosphere on the nature and extent of graphitization, and the possible correlation of graphitization with such characteristic properties as hardenability, grain size and mechanical behavior. In the present paper discussion is restricted to a study of the correlation between graphitizing tendency at 670°C. after quenching from several temperatures above the critical, and (I) the minor variations in the chemistry of these steels of "similar" chemical composition, and (2) the deoxida-tion practice employed. The state of the lead bath, oxidized or protected from oxidation by charcoal, used in the tempering treatments is also considered. Materials Eighteen plain carbon steels of about I per cent carbon, and containing similar amounts of each of the other common elements usually found as impurities, were obtained in the form of rods % in, in diameter from four steel manufacturers. The analyses for ordinary and special elements of all the steels were made on the rod stock as received in the laboratory, and the re-

Jan 1, 1941

By Park Wright

THE fact that granite has been encountered by the drill by those in search of oil and gas in Kansas is becoming more and more a matter of interest, not only to the oil producer but to everyone directly and- indirectly connected with the oil business. It is, therefore, time that someone should offer an explanation for its presence and form a definite opinion based on all the data available in regard to the effect it will have on the future prospects of the area affected as probable oil- and gas-producing territory. At present there seems to be no consensus of opinion. To the writer&apos;s knowledge, only one attempt has been made to explain; by Erasmus Haworth, State Geologist of Kansas, in a paper entitled Bulletin, Number Two on Crystalline Rocks in Kansas. The purpose of the present paper is to offer a theory for the presence of the granite and to draw conclusions which will aid in determining the prospective oil and gas value of the area in question. In taking up this question it will be well to consider first the tests in which granite has been reported, with a general history of each. The accompanying map (Fig. 1) shows the location of all wells described. The first well in which granite was reported was that drilled just south of Zeandale in section 27, township 10 south, range 9 east, by a local company which had taken up a block of leases in that vicinity. At a depth of 958 ft. (291.99 m.) granite was encountered. Drilling was continued to a depth of 1,093 ft. (333 m.) in the same formation, at which depth the hole was abandoned. Another well was started 1 mile east of the first well and the same rock was found at a depth of 945 ft. (288 m.). Drilling was continued to a depth of 1,200 ft. (365.76 m.) with the bit in the sane formation. Samples of the drill cuttings have been examined and they are undoubtedly crushed granite. The next well in which granite was found was that drilled by DeLaat and Shepard, independent wildcat operators, in section 34, township 19 south,. range 7 east, near the town of Elmdale. Granite was struck at 1,707 ft. (520 m.) and the hole was abandoned in the same formation at 2,525 ft. (769 m.). Mr. DeLaat watched the drilling of this well very closely and he has described to me in some detail the formation immedi-

Jan 8, 1917

By I. L. Dillamore

A purely geomentrical analysis based on oriented-growth relationships is presented to derive annealing-texture orientations in bcc metals from their- known deformation textures. The analysis takes as its starting point a description of- the bcc deformation texture and follows previous work on fcc metals in considering pvobable nurleation sites for recrystallization and the textural limitations on grains growing into a deformed matrix. The analy-sis accounts for the prominent and the minor coinponents of the annealing textures formed from two the deformation textures and can account for the ob-sem:ed temperature dependence of the annealing texture of bcc metals. THERE have been a number of investigations of annealing textures in bcc metals but few attempts to relate these textures to the deformation textures. This has been largely due to the lack of definition of both annealing and deformation textures, neither of which shows sharply defined orientations. It is, however, necessary to get a better understanding of primary recrystallization textures in bcc metals in view of increasingly exacting demands upon the quality of steel sheet for drawing purposes and as a necessary step towards the control of textures through processing. An analysis is presented here which relates annealing textures to deformation texture, by a purely geometrical method. This takes as its basis the oriented-growth theory of recrystallization and makes some reasonable assumptions regarding the make-up of bcc deformation textures and the limitations on growth relationships in bcc metals. Detailed information on this latter point is not available at the present time, and the present analysis may need to be streamlined or extended when such information is at hand. It is felt, however, that despite these limitations the analysis provides useful results and a valuable aid towards understanding the effect of processing variables. 1) BCC ROLLING TEXTURES Different workers have used a variety of descriptions for the texture developed in bcc metals by rolling. For the present purpose it will be assumed that two different deformation textures can be obtained: 1) a texture containing a major (112)[li0] component and a minor (001)[1i0] component for which increasing deformation causes the (001)[li0] component to increase at the expense of the (112)[li0] component, as suggested by Dillamore and ~oberts&apos; (this is the texture predicted to arise starting from randomly oriented material); 2) a t~xture containing the above components and (111)[110] and (ii1)[112] components. This texture could arise from a material with an initial (110)[001] or (iil)[112] texture. It is well-known that the (ll0)[001] orientation rotates to (ii1)[112]that on roll-

Jan 1, 1965