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By G. R. Speich

The precipitation of the Feab and Fe,Ti Laves phases (MgZn, type, C14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been studied in the temperature range 500" to 800°C using hardness measurements, light and electron microscopy, and X-ray and electron diffraction. The Fe-Nb alloys contained 0.96, 1.67, and 3.80 pct Nb and the Fe-Ti alloys 3.5, 5.8, and 8.8 pct Ti. In both systems only the equilibrium Laves phase is formed, with nucleation occurring at grain boundaries, at dislocations, and in the matrix. No cellular precipitation or transition phases were observed. The precipitation of the Laves phase in a fine dispersion leads to significant hardening in both systems. The hardness of the aged alloys is proportional to the reciprocal of the square root of the interparticle spacing. The maximum solid solubility of titanium in a! iron is 9.0 pct Ti at 1280°C. THE precipitation of the FezNb and FezTi Laves phases (MgZn2 type, C 14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been investigated as part of a continuing study of the mechanisms of precipitation from ferritic binary iron-base alloys. The iron-rich portions of the Fe-Nb and Fe-Ti phase diagrams are shown in Fig. l(a) and l(b). The Fe-Nb diagram is essentially that given by ansen' with the more recent work of Hume-Rothery and Gibson2 added. Goldschmidt3 indicates that the FezNb Laves phase has a solubility extending from 32 to 55 wt pct Nb. The Fe-Ti diagram is also essentially that reported by Hansen.l The recent results of Nishimura and kamei, Murakami, Kimura, and Nishimura,' indicate that the FezTi Laves phase has a solubility extending from 22.5 to 30.5 wt pct Ti. The L/6 + FezTi eutectic temperature of 1298°C indicated by Kornilov and oriskina' has been adopted. The addition of niobium or titanium to iron lowers the 6 — y transformation temperature and raises the y — a! transformation temperature. This results in a closed y field in the Fe-Ti system, but the lower solubility of niobium in a! (6) iron results in a eutec-toid, 6 — y + FezNb, at 1200°C, and a peritectoid, y + FezNb —-a, at 989°C in the Fe-Nb system. The maximum solubility of niobium is reported to be 4.5 wt pct in 6 iron,' 1.0 wt pct in y iron,7 and 1.8 wt pct in a iron.' Some results from the present work indicate that the maximum solubility in a! iron is actually less than 0.96 wt pct Nb. The maximum solubility of titanium in a! (6) iron is somewhat uncertain since the early work of To faute and Butting-haus indicated a value of 6.0 wt pct while later work of Kornilov and Boriskina6 yielded a value of 14.0 wt pct. The present work indicates that the maximum solubility is actually 9.0 wt pct. In both systems the phase in equilibrium with the iron-base solid solutions is a Laves phase (Mg znztype, C14), FezNb or FezTi. Both of these Laves phases have a wide range of Solubility. The precipitation-hardening behavior of Fe-Nb or Fe-Ti alloys has not been studied extensively. Genders and Harrison' reported that binary Fe-Nb alloys hardened upon aging. Peter and Fisher7 studied the mechanical properties of Fe-Nb and Fe-Ti alloys quenched from different phase fields.

Jan 1, 1962

By I. R. Kramer

The stress associated with the high-dislocation layer at the surface of deformed aluminum crystals was measured by progressively polishing the specimen and determining the change in the initial flow stress when the specimen was reloaded. This surface stress increased linearly with strain in the Stage II and Stage III region. The depth to which the high-dislocation layer extends was found to be 0.0025 in. The influence of the surface layer on Stage I is discussed and it is shown that Stage I ends when, on the secondary slip system, the difference between the applied stress and the opposing stress due to the surface layer is equal to the critical resolved shear stress. In previous papers'-3 it was shown that the surface exerts a pronounced effect on the plastic-flow characteristics of metals. For fcc metals it was possible to increase the extent and decrease the slope of Stages I and II and decrease the work-hardening coefficient of Stage II by removing the surface of the specimen continuously during the deformation process.2,3 More recently,L it was shown that the activation energy for plastic deformation and the activated volume were also influenced by the surface. These changes were related to the existence of a high concentration of dislocations in the region near the surface of the deformed specimen and it was concluded' that the effective stress, T, acting on a dislocation was T = Ta-Ti-Ts [1] where 7, is the applied shear stress, Tj is the internal stress, and TS is the stress associated with the surface region containing the high concentration of dislocations. From Eq. [I] it is seen that the effective stress, 7, acting on a dislocation is a function of 7,. Therefore 7, becomes important in any description of the work-hardened state. In this paper the value of 7, as a function of strain and its variation with depth are reported for aluminum single crystals. In particular, it will be shown that the end of Stage I occurs when the net stress, 7, on the secondary slip system is equal to the critical resolved shear stress. To measure Ts, single crystals of aluminum were deformed in tension to various strains, whereupon the load was removed and a known amount of metal was removed by electrolytic polishing. The differ- ence between the final flow stress before the specimen was unloaded and the initial flow stress upon reloading is designated as ?Tp and is the decrease in the stress due to the removal of the surface layer in whole or in part. The value for Tp is taken equal to -Ts. EXPERIMENT PROCEDURE The details of the tensile apparatus, method of electrolytic polishing, and crystal preparation were the same as those used previously,1"3 The single crystals were 1/8 by 1/8 in. in cross section with a 3-in. gage length. The initial purity of the aluminum was 99.997 pet. The specimens were held in vacuo at temperatures 50°C below their melting points for 16 hr and furnace-cooled. Just prior to the application of the tensile stress the specimens were electrolytically polished to remove 0.004 in. from the thickness. This latter operation was conducted after the specimen was placed in the tensile apparatus. The tensile tests were conducted at a strain rate, i, of 10"5 sec-' and a temperature of 3°C. The aluminum crystals used for the determination of 7, are designated A1-3-12 and A1-116. The orientation of the various crystals used throughout the investigation is shown in Fig. 1. The ?Tp values for specimens A1-3-12 as a function of Ax were determined mainly at four strain levels, i.e., ? = 0.0217, 0.0381, 0.0593, and 0.075, where Ax is one half of the total reduction of the thickness after polishing and ? is the re-

Jan 1, 1965

By J. Lindbo, B. Vigeholm

IN transmission electron microscopy, specimen thicknesses quoted are frequently based upon either traditionally familiar values or a few evaluations representing the whole material. Taking aluminum in 100 kv TEM as an example, average and maximum values are widely accepted as being 2000 to 2500 and 6000 to 7OOOÅ, respectively. It is the purpose of this note to revise these figures and to point out the importance of evaluating individual specimens carefully. All evaluations have been based upon slip trace widths and lattice orientations as determined from diffraction patterns. In many cases where two or more slip systems have been operating the geometrical method described by Crocker and Bevis1 has been applied as a check. The foils were usually oriented to within 2 deg from the exact Bragg angle. Kikuchi patterns were used as indications of correct orientations but not applied in the evaluations. The tilt of the foil surface relative to the beam normal may with certain geometrical relations between the tilt axis and the operating slip plane lead to substantial errors.2'3 Where these geometries were inevitable the samples were omitted in the investigations. Various measures were taken in order to overcome ambiguities, e.g., comparison with neighboring grains, tilts, evaluations based upon two or three slip systems,' and comparison with extinction contour evaluations where s = 0 conditions were obtained. Errors caused by misinterpretation of the slip traces on a micrograph are easily avoided by considering the bright-dark sequence on opposite surfaces and by taking into account the tapering of the foil usually leading to a distinguishable divergence of the pair of traces. In the investigations described here the interpretation was further facilitated as the slip trace formation was observed on the microscope screen and sketches taken down. In a few observations slipping was so violent that the distinction of pairs was considered dubious and consequently given up. To assess average values, thickness evaluations carried out in two independent investigations were analyzed: I) 99.998 pct A1 extruded, cold-drawn, and recrys-tallized to grain sizes between 35 and 500 um were deformed in tension at room temperature. In order to determine the dislocation densities as a function of strain,4 specimens prepared by spark machining and electropolishing in a PTFE holder were analyzed in the electron microscope at 100 kv. Thicknesses were evaluated for 569 selected areas. Histogram I in Fig. 1 shows the results, the average thickness being 4900Å. II) Electropolished specimens prepared from 99.9999 pct A1 with magnesium contents from 0.005 to 0.5 pct rolled to foil and annealed were subjected to fission fragment irradiationa2 For volumetric dose and defect concentration determinations thickness evaluations were performed on 123 areas. Histogram II in Fig. 1 shows the thicknesses of these areas averaging 4250Å. Whereas in investigation I no selection related to thickness has been made, some thin as well as thick areas have been omitted from I1 for experimental reasons. This and the application of two different microscopes although of the same type may account for the difference in average thickness. Assuming a mean error of 10 pct for a single evaluation, the error of the average should be negligible. In order to investigate the maximum transmissible foil thickness in aluminum, specimens were prepared from single crystals with (111) and (110) orientations parallel to the beam, and from polycrystalline material. Maximum values of thickness that could be measured were given by the stopping of the dislocations. The visibility often extended far beyond the end of the slip trace, but with no means of knowing the

Jan 1, 1970

By S. E. Haszko

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKa radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuA12 and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band. 1,4 Europium in EuAl2, appears to have a valence closer to 2. In previous work.' X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref 1. One of the other phases was identified as Co,Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. 'J. H. Wernick and S. Geller: AIME Trans., in press. 'J. H. Wernick and S. E. Haszko: to be published. 'F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. 'S. E. Haszko: to be published. 'J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acla Cryst., 1959, vol. 12, p. '162. The Influence of Hydrogen on the Lattice Parameters of Ti-Sn Alloys A. Coucoulas and H. Margolin A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently higher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961

By Norman F. Schulz, Emert W. Lindroos, Strathmore R. B. Cooke

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By C. A. Fothergill

An improved blotter model is described which makes use of a plastic sheet as base for the blotter field and pins to represent the input wells. The model is simple to construct and adapt and is particularly useful for demonstration purposes. Operational details are given. INTRODUCTION The blotter model was first applied to the investigation of oilfield problems by Wyckoff, Botset and Mus-kat,' primarily in order to demonstrate the flood patterns which could be expected from various arrangements of input and output wells in waterflooding projects. In recent years the model has been largely superseded for analog studies by the potentiometric and electric analog models which are more refined and versatile, since they can simulate the form, and, in certain cases, permeability variations which it is not possible to do with the blotter model. However, the latter is still used for analog studies where the reservoir can be represented as being uniform in thickness and permeability, and where a visual record of the flood advance is required. Ramey andNabor,2 for example, have applied the model to the investigation of areal sweeps in oil recovery by in-situ combustion. Because of its limitations, the blotter model can be used in general for only very simple arrangements of input and output wells, but within these limitations it has a definite advantage over all other types, in that it provides a picture of the advancing flood using the simplest and most easily constructed apparatus, by contrast with the gelatin model, for example, which requires more elaborate equipment. Moreover, the experiments can be quickly repeated and modified if necessary, whereas considerable time is required to prepare a gel field, compared with that required for the preparation of sheets of conducting blotting paper. For these reasons the blotter model can be very useful for demonstration and teaching purposes, enabling the student to experiment for himself with different arrangements of input and output wells. A model has been constructed for this purpose which is simple to operate and adapt. The model (Fig. 1) consists of a base platform or box, approximately 12-in. square, on top of which are screwed three lathes of 1/2 -in. square section to form three sides of a square 6 in. in length. This forms the support for a sheet of Cobex, transparent plastic, thickness .003 in., on which is carried the blotting paper representing the field. The plastic is flexible and relatively soft, and can be attached to the support by cellulose tape so that it can be easily removed when required. The input wells are represented by brass drawing pins pressed through the plastic sheet from the underside until the points are just projecting through the top; these are connected in the circuit as shown in Fig. 2. The sheet of blotting paper of required shape and size is saturated with a solution of 0.2 n-potassium sulfate to which has been added a saturated alcohol solution of phenol-phthalein at a strength of 10 cc/liter of stock solution. The surplus water is removed and the blotting paper placed in position on the plastic sheet making contact with the drawing pins and the sheet (which is an insulator). The anode consists of a second sheet of blotting paper cut as shown and saturated with the same solution. This is suspended from a laboratory stand, being connected to the conducting wire by means of a crocodile clip and making contact with the horizontal blotting paper at the projecting point. This is the method used by Ramey and Nabor and which permits the hydroxyl ions or colored front to reach the anode. As shown in Fig. 2, the electrical voltage used is 220-v DC and a shunt is placed across the terminals to step down the voltage as required. Further adjustment can be made as necessary using a lamp board in series with the shunt to obtain the

Jan 1, 1958

By H. Margolin, A. Coucoulas

Fused alumina or silica crucibles were used as the containing vessel. X-ray powder photographs were taken with CrKcll radiation and the use of Straumanis type Norelco cameras of 114.6 mm diam. Crystallographic data for these compounds are shown in Table I. These results are in agreement with others of this series reported previousiy by Wernick and Geller.l The abnormally large atomic volume of Eu and Yb metal3 is manifested in EuAl2, and YbAl2, when one compares them with the compounds reported in Ref. 1. However, the behavior of Yb in the Ni compound is the same as that observed in Ni5Yb having the Cu5Ca structure.4 Thus, it appears that Yb has a valence closer to 3 only in the Ni compounds; i.e.. the 2s and Id electrons are lost to the conduction band.1,4 Europium in EuAl2 appears to have a valence closer to 2. In previous work.' X-ray patterns of ingots of NdCo2 indicated a multiphase material with faint indication of the presence of a phase having the MgCu2 structure. It was thought that NdCo2 formed peri-tectically from the melt, resulting in a multiphase system when cooled under nonequilibrium conditions. An X-ray pattern of a sample from a melt cooled more slowly than in past work showed that the major phase was NdCo2. The lattice constant, Table 1, is in excellent agreement with the value one can predict from the data of Ref. 1. One of the other phases was identified as Co5Nd. The author wishes to thank J. H. Wernick for his guidance in this work, and D. Dorsi for the preparation of these compounds. 'J. H. Wernick and S. Geller: AIME Trans., in press. 'J. H. Wernick and S. E. Haszko: to be published. 'F. H. Spedding and A. II. Daane: Progress in Nuclear Energy, Series 5, Eds.: H. M. Finniston and J. P. Howe, McGraw-Hill Book Co., 1956. 'S. E. Haszko: to be published. 'J. H. Wernick and S. Geller: unpublished work. 6J. 11. Wernick and S. Geller: Acia Cryst., 1959, vol. 12, p. '162. A reinvestigation of the lattice parameters of Ti-Sn alloys by the present authors has revealed consistently hiher c and a values than those obtained by Worrier. The difference is most pronounced in the c-parameters which are, therefore, used as a basis of comparison. This discrepancy was not due to air contamination, since precautions were taken to exclude this possibility. Specimens for Debye-Scherrer photograms were prepared by arc-melting 15-g buttons of Bureau of Mines titanium and 99.99 pct Sn, with compositions of 6, 8, 10, and 12 at. pct Sn. These buttons were forged under an oxygen-acetylene torch to 1/8-in. sq rods to produce relatively fine grained material. Scale and some surface were ground off, and the rods, after wrapping in molybdenum and titanium sheet, were vacuum annealed 15 min at 800 °C to remove hydrogen. Heat treatment of one of the samples at 875°C to produce ß and reveal a at the surface showed no surface contamination. Following the vacuum treatment, the specimens were wrapped in molybdenum and annealed for 1 week at 800°C under two atmospheres of argon. After water-quenching, the rods were ground so that the thickness tapered to 0.1 mm at the tips. The ground specimens were then recapsuled as previously and reannealed 1 hr at 800°C to remove cold work. The

Jan 1, 1961

By Strathmore R. B. Cooke, Emert W. Lindroos, Norman F. Schulz

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (-—CH,CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder" has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate—potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality. of the preparation of the aminoethyl starch: "Three hundred and sixty grams of powdered unmodified corn starch was slurried in 3 liters of water and stirred during gelatinization. Eighty-six grams of ethylenimine was added slowly during reflux which was continued for 4 hr. The yellow solution set to a gel upon cooling. This was broken up and neutralized with HC1. The thick paste was dried on hot rolls. Adsorbed polyethylenimine and salts were removed from the yellowish products by washing first with acidified aqueous '60 per cent' alcohol. The white product contained nitrogen corresponding to about one aminoethoxy group per ten glucose residues." Only laboratory samples of this starch derivative have been prepared. The starch reagents for use in flocculation, flotation, and adsorption tests were made up by dispersing the appropriate quantities of air-dry starch in cold water, adding boiling water, and heating for 30 min at 120°C under pressure. When used ip adsorption tests, the starch solutions first were cleared of insoluble matter by centrifugation.

Jan 1, 1953

By Eugene McAuliffe

SINCE 1917, the bituminous coal industry has surged, violently at times, across the nation's social, industrial and economic foreground. To-day a silent, yet more active, force is working within the industry, and the movement now taking place, if allowed to continue, will cause serious consequences when coal is again wanted at the rate of 550,000,000 tons annually instead of at the rate of 400,000,000 tons, the apparent requirement for 1921. I refer to the shift of tonnage from the highly unionized fields of Pennsylvania, Ohio, Indiana and Illinois to the non-union fields of Pennsylvania, West Virginia, Alabama and certain western states, and to the so-called union fields in Kentucky and Colorado, on which the union saddle rests lightly. This movement, in the absence of the usual winter transportation shortage, is taking place rapidly and will be accentuated if, as is probable, work is suspended in the union mines on March 31 next. This drift of tonnage has been made possible by the unit wage reductions in the non-union fields and by the modification of the so-called conditions that have been saddled on all mines wherever the United Mine Workers have gained a foothold; these changes permitted the first reduction in mine cost, which made possible the securance of contracts; better running time assisted in making further reductions, and the transfer of ton-nage served to increase the unit cost in the field from which it was transferred. This situation not only opposes the highly unionized operation but brings about a transfer of traffic from the roads serving such mines to those that serve in a primary or secondary manner the more favored localities. The net result is evidenced in (a) the migration of union labor to the non-union mines; (b) the deteriora-tion and decadence of union properties; (c) the neces-sary curtailment in the purchase of new equipment and in the maintenance of existing equipment and track facilities on the part of the carriers serving the union fields. This, in turn, when business is restored to normal or to the point above normal that invariably follows an adverse swing of-the business pendulum, will cause (d) a shortage of coal and coal transportation facilities; (e) an era of coal speculative debauchery with exorbitant prices and serious deflection in the matter of quality; (f) a period of labor unrest followed by de-mands for increased wage rates supplemented by a marked loss in individual efficiency, with, resultant strikes, business unrest, and the pressure of new eco-nomic theories. In 1918, the labor status with respect to relative tonnage produced was approximately as follows: pro-duced in highly organized fields, 62 per cent.; produced in partly organized fields, 21 per cent.; produced in unorganized fields, 17 per cent. During the strike of November and December, 1919, the mines that remained at work attained 35 per cento of the nominal production of soft coal, a situation made possible by the migration of union labor to non-union mines and the concentration of the nation's coal trans-portation facilities on the rails of the carriers serving the non-union fields. The history of the efforts made by the carriers to untangle the car scrambling which took place during this period and which sent the self clearing battleship type of car into western territory where it could not be readily unloaded, and the western gondola type of car to New England and the seaboard, is yet painfully recalled. -This confusion proved a serious factor in the coal car shortage that continued throughout the following year. We are drifting toward a similar situation now, propelled by economic forces rather than by a sudden strike.

Jan 1, 1922

By G. S. Coe, G. F. Bolling

The columnar-to-equiaxed transition (CET) has often been studied as a function of concentration, C, temperature gradient in the melt, G, and rate of solidification, R. Although it may not be immediately obvious it is sure that the CET, expressed as some ratio G/R necessary to suppress equiaxed nucleation for a given C,' cannot be a single-valued function of C. This restriction which is ignored in theoretical presentations is most trivially illustrated by the following simple reasoning. An ordinary casting is an unconstrained system where the thermal conditions change continuously with progressive solidification, and thus where the ratio G/R decreases from the outset. A CET occurring early in a casting (much equiaxed material) must then mean a higher value of G/R at transition, in comparison with the late CET which implies a more columnar ingot. Therefore, when we choose to experiment under constant superheat for all alloys across the simplest binary, and we find an inversion in the amount of equiaxed material, we shall find two values of C satisfying the G/R condition. However, in addition to this simple instance, the early experiments of ~orthcott' seem to show that the amount of equiaxed material in cast ingots may be a multivalued function of composition in a given binary system. In the present investigation, the CET has been examined in Pb-Sb, Pb-Ag, Pb-Sn, and Sn-Pb under several types of casting conditions. First, we have used the "bidirectional" ingot section Simulation;~ and we have used .'i~z situ" ingot solidification where a hot mold already filled with liquid is chilled so that there is no disturbance provoked by pouring. Differences in method are trivial to our purpose except for the fact that certain variations are more simply observed by one technique than by the other. Second, we have varied the mode of superheating from the simple extreme of casting all alloys from the same temperature regardless of composition to the careful casting at a standard superheat, calculated with respect to the alloy liquidus. Third, we have made provisions for decanting and interface observation, so that some "castings" were not completed. The results obtained with Pb-Sb are exemplary; some of these are shown in Fig. 1 along with explanatory captions. At 9 to 10 at. pct Sb, and thus above the solid-solubility limit Cs = 5.8 at. pct Sb and yet below the eutectic concentration Ceu = 17.5 at. pct Sb, there is a persistent anomaly in all the variations. Measurement was easy enough and standard enough so that we may forgo discussion of either method or possible error, in view of the forceful self-consistency shown by experiment. Solute distributions were measured along the bidirectional ingots in order to determine if a solute buildup had occurred at the CET. No anomalous changes in concentration were observed along the bars at either side of the solute anomaly of 10 at. pct Sb. The microstructures of the ingots were also examined across the range of composition investigated. At concentrations less than 9 at. pct Sb the micro- and macrostructures were typical of the cellular-dendritic growth usually reported for the columnar zone. Above the anomaly, both the columnar grain size and the amount of primary phase decreased. This microstruc-tural observation can be correlated with observations made of decanted interfaces. Below 9 at. pct Sb, the interface reveals the "normal" columnar dendritic structure; however above the anomalous concentration range, preferential growth of certain dendrites appears to form a "super dendrite" pattern. In Fig. 2 a microstructural view of the etched '(super dendrites'' shows their constitution both in terms of relative phase proportion and in terms of the ordinary smaller dendrites.

Jan 1, 1969

By Richard Franchot

DISCUSSION of a paper is sometimes more in-teresting in what has not been said than in what is said. In the present case the paper is mainly directed to certain thermo-dynamic relation-ships in the blast furnace. Careful reading of the dis-cussion fails to show a single use of the term, heat unit, or its equivalent. If we wish to know very-much about the furnace action it is necessary to count calories or B.t.u. Nothing much is. said about the availability of heat at high temperatures, although it will be generally admitted that in seeking underlying limiting factors in the furnace economy the hearth heat relations offer-the most promising clues. Those discussing the paper, with exceptions of course, apparently have failed to recognize an outstand-ing fact. It is a fact that the heat actually generated by the air oxygen in CO formation (including the blast heat) is in excess, after charging off radiation, etc., by from 70 to .90 per cent over the heat absorbed in melting the iron and slag and calcining the stone reduction by CO absorbing no heat. The fact stands out as plainly as does the fact that the furnace functions largely as a gas producer. The surplus heat is there. It is in the picture. Why not take a look at it, face the fact? That the surplus heat is necessitated by the hearth conditions admits of very little if any doubt. The furnace is really two separate pieces of apparatus: the hearth, doing certain work, and the superimposed shaft, doing certain other work. The combustion of fuel in the hearth, primarily serving the hearth pur-poses, generates much more heat and gas than the shaft requires, or can use, in smelting work. The result is surplus heat makes still more gas in the heat-absorbing reaction between CO, and coke; what is left of the surplus going to top heat. Here we have a simple yet adequate sketch of the furnace action. Having obtained a fairly comprehensive view of the existing heat relations of both hearth and shaft, the way to improvement seems quite plain. Either do more of the work above the hearth or put more heat into the hearth. Since there is already a great surplus of heat above the hearth, probably little needs to be done by way of increasing the proportion of the work done in the shaft. The shaft can, however, probably do much more work than it is now doing provided that a way, can be found to get more work, done in the hearth. The hearth heat is nicely balanced. Losses by radiation and water cooling and other losses are already taken care of. Any increase of hearth heat development could be utilized in taking care of increased smelting work. Aside from the possibility of increased blast heat, there is one sure way of putting more heat into the hearth, and this is to blow more air. And since the shaft already has more gas than it needs, the increased gas resulting from the greater blast volume can be withdrawn from the bosh after it has done its work in the hearth. Now an increase of burden will cool the shaft, cut down solution loss and thereby supply addi-tional coke in the hearth to burn with the additional air blown. The hearth heat per pound of coke charged will be proportionately increased. The balance between hearth and shaft will be better. Gruener's ideal will be more nearly attained, if not exceeded. Most inter-esting of all perhaps, the more the burden is increased, the more coke will reach the hearth and the more burden can be added. The effect is to be cumulative.

Jan 3, 1927

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs.' Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster" and was first reduced to practice by the experimentation of Welge. In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid Phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always ereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By Walter Rose

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs. Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster and was first reduced to practice by the experimentation of Welge . In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize Welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always gereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By P. T. Bail, J. E. Bobek

In reservoirs containing soft shales interbedded with oil-producing sands, it is possible to have water movement from the shales into the sands during reservoir depletion. This paper presents the results of scaled flow-model tests performed to investigate the efficiency of oil displacement by this vertical influx of water into oil-producing sands. In these model tests, the effects of rate of influx and rock wettability were considered. Oil recoveries by shale-wafer influx and by water flooding were cornpared after 0.4 hydrocarbon volume of water entered the producing sand. This comparison was made for water-wet and oil-wet systems. In water-wet sand, shale-water influx produces slightly less oil than conventional water flooding; in oil-wet sand, shale-water influx produces about one-half as much oil as conventional water flooding. In another type of comparison, it was found that shale-water influx followed by water flooding recovers less oil than water flooding alone. This is true for both water-wet and oil-wet sands. A comparison of tests run at different rates of shale-water influx shows that oil recovery is insensitive to rate in water-wet sand; in oil-wet sand, oil recovery decreases with decreasing rate of influx. INTRODUCTION Localized subsidence of the earth's surface has accompanied the depletion of some oil reservoirs, particularly in California,1, 2 along the Texas Gulf Coast,3 4 and in the Bolivar Coastal fields of Venezuela. Subsidence occurs when fluid withdrawals reduce the pressure in the reservoir. The reasons for subsidence accompanying a reduction in reservoir pressure are not known with certainty.10° However, there is considerable evidence that compaction of soft shale beds adjacent to producing oil sands can be a major cause of this subsi-dence.3, 6, 10-12 When the shales compact, a limited amount of water moves from the shales into the producing sands. A schematic illustration of this oil-producing mechanism is shown in Fig. 1. As the pressure in the sand declines due to oil production, a predominantly vertical pressure gradient develops at the sand-shale boundary. This causes water to move from the shale into the sand as indicated by the solid arrows. This paper reports the results of scaled flow-model tests to investigate the efficiency of oil displacement by the vertical influx of shale water into producing sands. The model tests were not performed with the aim of duplicating the recovery behavior of any specific reservoir. The primary purpose of the tests was to obtain a better understanding of oil displacement by shale-water influx. A knowledge of the oil- and water-production characteristics of even a simplified reservoir system should be of value to engineers estimating the performance of reservoirs where shale-water influx is occurring in conjunction with other production mechanisms. The following limitations and assumptions apply to the model work. 1. The sand of the prototype reservoir is homogeneous and horizontal. 2. The shale-water influx is uniformly distributed along the top and bottom of the sand member being studied. 3. No effects of edge-water drive or dissolved-gas drive that might accompany shale-water influx are considered. PROTOTYPE RESERVOIRS Scaled-model tests were performed to study oil displacement from three prototype reservoir sections. The reservoir sections modeled consist of single sand layers out of a sequence of -sand and -shale layers, as illustrated in Fig. 1. Each prototype represents a homogeneous, high-permeability, unconsolidated sand layer. In the field, the prototype is oriented in such a manner that one end is at the radius of drainage of a producing well and the other end is pointed toward the producing well (Fig. 2). The sand and fluid properties and the dimensions of the three prototypes are given in Table 1. The capillary pressure relationships for the three prototypes are presented in Figs. 3, 4 and 5. The oil-water per-

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs.' Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster" and was first reduced to practice by the experimentation of Welge. In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid Phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always ereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By R. S. Wagner, H. Brown

Criteria for nucleation with the aid of twin planes during crystal growth from the melt are discussed. It is shown experimentally that bismuth crystals can grow from a subercooled melt in a twinned bismdtic form. A mechanism of growth based on the presence of at least me twin plane is proposed. It is well known that faceted growth can be observed in crystals grown from the vapor phase, dilute solutions, or from the melt. Faceted growth, in which the crystal is bounded by its slowest growing faces, will occur if the growth rate is strongly orientation dependent. The addition of atom layers on a facet plane can only occur by two-dimensional surface nucleation or with the aid of an imperfection. Nucleation with the aid of dislocations was proposed by rank' and observed to be of particular importance in crystal growth from the vapor phase. Nucleation with the aid of two-dimensional imperfections, notably twin planes, was suggested by stranski2,3 and Frank.4 A twin plane, terminating at the growth interface, can form a reentrant step at which nucleation can occur at a much smaller super-saturation (or supercooling) than required for two-dimensional surface nucleation. Nucleation by a twin plane usually results in a fast growth rate along a crystallographic direction parallel to the twin plane. Such a nucleation mechanism, based on the presence of a twin plane, has been used by Dawson5 to explain the growth and morphology of sheet-like crystals of paraffin n-hectane. In recent years more evidence was found that nucleation by twin planes occurs frequently in crystal growth from the vapor phase and from dilute solutions, for example, in cadmium,' barium titanate,7 silver,8 silicon9 and gallium arsenide.10 In crystal growth from a supercooled melt, however, nucleation by twin planes has so far only been observed in materials with the diamond or zinc blende structure. Bennett and Longini11 were the first to recognize the important role a single twin plane plays in the growth of germanium dendrites. Subsequently, it was found that a prerequisite for continued propagation of germanium dendrites is the presence of two parallel twin planes which form a self-perpetuating system of nucleation sites.12 Sili- con and some III-V compounds such as InSb also grow dendritically by twin plane nucleation. It appears that the following criteria must be satisfied in order that nucleation with the aid of twin planes can occur: A) The growth form of the material must be faceted." B) The formation of twin boundaries, by a fault in layer sequence during growth, by plastic deformation, or by an accidental meeting of properly oriented crystals, must be possible. C) Twinning must form a reentrant step where the twin boundary terminates at the faceted growth interface. D) These three conditions are necessary, but in certain cases not sufficient for continued crystal growth with the aid of a twin plane. Depending on interface morphology, a combination of more twin planes is sometimes required to form a self-perpetuating system of nucleation sites. This investigation was carried out with the idea in mind that nucleation with the aid of twin planes is a more general phenomenon and should occur in those materials, grown from a supercooled melt, which satisfy the criteria outlined above. It has been found that crystals of high-purity bismuth grown from a supercooled melt can grow by the aid of a twin plane. In the first two sections the faceted growth form and the twinning elements of bismuth are discussed. In the last section prismatic crystals of bismuth, which appear to grow with the aid of a deformation twin are discussed.

Jan 1, 1962

By J. P. Hammond, C. J. McHargue, S. E. Adair

Cold-rolled sheet textures have been determined for binary solid solutions of aluminum, columbium, tantalum, and zirconium in titanium. An alloy containing 3.8 pct Al had a (0002) [10101 texture, whereas alloys with the other elements had rotated (0002) [10101 textures similar to that of iodide titanium. THERE have been relatively few studies of the effect of alloying on deformation textures. A second element may be present in the base metal in solid solution and/or as a second phase. The literature offers no satisfactory explanation for the effects of solid solution alloying on textures noted thus far. For example, there is no satisfactory explanation of the difference in the textures of copper and a brass. The most complete study of the effects of solid solution alloying on deformation textures has been that of Brick, Martin, and Angier.¹ These investigators reported that the copper texture was retained by alloys of copper with up to 30 pct Ni, less than 5 pct Zn, less than 2 pct A1 or Co up to the limit of solubility. Copper containing more than 5 pct Zn, more than 2 pct Al, or the maximum soluble concentration of tin, silicon, or manganese showed the deformation texture of a brass. Bakarian² reported that additions of 0.20 pct Ca to 99.98 pct Mg or 2.0 pct Mn plus 0.15 pct Ca to magnesium resulted in entirely different textures than for the pure magnesium. The texture obtained for high-purity magnesium sheet showed the basal plane to be concentrated parallel to the rolling plane. The texture obtained for the alloy containing 0.20 pct Ca had the basal planes concentrated in elliptical areas whose centers were tilted 15" from the center of the pole figure toward the rolling direction. This split basal orientation was even more pronounced in the alloy containing 2.0 pct Mn and 0.15 pct Ca. Fuller and Edmunds" studied the rolled sheet textures in a zinc alloy containing 1 pct Cu and 0.01 pct Mn. The basal pole figure of this alloy contained a region of strong concentration not found in the pole figure for pure zinc.' In the above cases, results were discussed in terms of possible changes in slip and/or twinning systems and critical shear stresses. However, there were no experimental data to relate these speculations with the observed textures. It has been suggested that the deformation textures of titanium, zirconium, and beryllium could be directly ascribed to their low c/a ratios. The complex deformation mechanisms of titanium" also have been suggested to be characteristic of hexagonal close-packed metals with low c/a ratios. The purpose of this investigation was to study the cold-rolled sheet textures in binary titanium-base a alloys in which the c/a ratios were greater than, less than, and about the same as the c/a for iodide titanium. The annealed textures of these alloys will be reported in a subsequent article. Materials and Methods The chemical analyses of the metals used in this investigation are given in Table I. The alloys were prepared as 15 g buttons on a water-cooled copper block in a vacuum arc-furnace. The furnace was evacuated to pressures of the order of 10.' mm Hg, flushed with 99.98 pct pure argon, and melting was carried out in 0.2 atm pressure argon. Each button was remelted until radiographs and chemical analyses indicated complete solution of the solute elements. All buttons were forged and homogenized 72 hr at 500°C. The buttons to be rolled were ground and etched to sizes and shapes suitable for the rolling

Jan 1, 1954

By T. J. Whalen, M. Humenik

The liquid surface tension of copper-nickel ad copper-nickel-titanium-carbon alloys and the wettability of titanium caybyde by these alloys have been measuhed. It was found that the surface tensions of the binary copper-nickel alloys Lie on a smooth curve between the end members, copper and nickel. The addition of small amounts of titanium and carbon has nO effect on the surface tensions of copper-nickel alloys. Small additions of nickel to copper significantly reduce the contact angle of Ike alloy with titanium carbide. From a Gibbs treatment, nickel is shown to be adsorbed at the titanium carbide-alloy interface. X HE microstructure of two-phase materials has been shown to be influenced largely by the interfacial energies between the phases present.' , In systems prepared by powder metallurgy techniques and densi-fied in the presence of liquid phase, a precise analysis of microstructure and interfacial energy relationships requires a knowledge of the solid-solid interface energies and liquid-solid interface energies. However, marly metal-nonmetal systems are characterized by the "sweating" of the liquid during sintering, and in these systems wettability is a principal consideration. The wetting in turn is dictated by the various interface energies of the system, as shown in Fig. 1 for a liquid drop formed on a solid substrate. The equation which expresses the vectorial balance of surface forces in the horizontal plane, at the point of contact, A, is given by: where ssv = solid-vapor interface energy sSL = solid-liquid interface energy sLV= liquid-vapor interface energy 6 = contact angle measured through the liquid phase. The angle and the surface tension, slv, can be measured accurately by the sessile drop method.3, The absolute value of the surface energy of the solid cannot be determined by this method, but with reasonable changes in the composition of the liquid only, the value of ssv can be considered constant. The changes in contact angle, then, can be attributed to changes in sSL and sLV and since sLV can be measured, the changes in sSL can be determined. Several studies have indicated that the surface and bulk properties of solid alloys can be correlated with electronic structure. The catalytic activity of copper-nickel alloys was reported to follow the dband vacancies in these alloys.5 Nickel has been considered to have 0.6 holes per atom in the d-band. The addition of copper to nickel is thought to bring about a filling of the d-band of nickel, since each copper atom contributes one electron. Thus, at an atomic concentration of 60 Cu-40 Ni (62 wt pct Cu-38 wt pct Ni) the d-band is believed to be full, and magnetic measurements support this view.6 If the electronic structure is influencing a property of the alloy, this property should show some sort of discontinuity as the composition changes from one side of the 60 Cu-40 Ni composition to the other. Since the catalytic activity can be considered as a surface property of the alloy, it is logical to assume that other surface properties, such as surface tension, may also be influenced by electronic structure. The suggestion has been made that there is a correlation between the solid titanium carbide-liquid Cu-Ni alloy interfacial energy and d-band filling.7 One purpose of this investigation was to determine if the changes taking place in the electronic structure with compositional changes in the solid copper-nickel alloys were reflected in the surface tension values of the liquid alloys. Such a change, if present, would lend support to the suggestion that one can refer to discrete energy bands in the liquid state. Other purposes of the present study were to investigate in detail the wettability in the system copper-nickel-titanium carbide, and to discuss the possible processes which take place during wetting in this system.

Jan 1, 1961

By Walter Rose

Experimentation which measures differences in pressure across the interfaces of immiscible fluids in the interstitial spaces of porous media may be termed "capillary pressure experimentation". In the literature of petroleum technology since 1941 there have appeared twelve papers popularizing capillary pressure concepts and developing applications of these concepts for the solution of problems of practical reservoir engineering importance, such as the determination of connate water, fluid distribution. in transition zones, reservoir rock textural properties, and oil recovery from petroleum reservoirs. Although a review of the literature would be justified at this time in order to reconcile the conflicting viewpoints which are contained in the cited papers, the object of this note will be of more limited scope. It is believed that the recent paper of Muskat alls sufficient attention to many of the uncertainties which arise upon examination of the published literature. such that until satisfactory counter-proposals can be made it will serve our purpose only to mention some other like uncertainties. This will emphasize further the need confronting petroleum technologists to re. consider and reformulate the application possibilities of capillary pressure experimentation. In particular, I sug- gest that we examine the thesis that capillary pressure experimentation as above defined can lead to measurements reflecting the recovery of oil from petroleum reservoirs, as was proposed first" by Amyx and Yuster and was first reduced to practice by the experimentation of Welge . In fact. I shall deal exclusively with the Welge papers since it is the principle one on this subject which has appeared to date. I shall attempt to show that the possibility of describing oil recovery features in terms of capillary pressure phenomena has not been established entirely. The Welge paper was a pioneering effort to evaluate this recovery application possibility. P. P. Reichertz' comments on the Welge paper state that non-wetting phase discontinuities are developed occasionally in the Welge experiment, and restate Muskat's argument that discontinuous fluid elements (partially saturating the interstices of porous media which are elsewhere saturated with some other immiscible phase or phases) are not subject to the requirements of hydrostatic equilibrium. It is the purpose of my comment to show that it is unnecessary to make Reichertz' postulation regarding non-wetting phase discontinuities (however valid) when it is desired to criticize Welge's theoretical treatment of his problem. It can be shown that Welge's method of measuring values for ''capillary pressure" is invalid in many instances of application, such that his reported curves of capillary pressure Versus fluid saturation often have no physical meaning, even throughout the interval of fluid saturation where it might be otherwise suspected that no phase discontinuities occur. By considering established principles of capillary pressure experimentation it can be shown that the pressure difference experimentally observed between wetting and non-wetting fluid phases which are contained in external reservoirs will reflect on the capillary pressure difference at the interfaces of contact between these phases only when the following conditions are satisfied: (a) There shall be a balance between the opposing forces of gravity and capillarity, as obtains under conditions of hydrostatic equilibrium when the positions of the interfaces of contact become fixed in pore spaces of certain geometry (b) The wetting and non-wetting fluids within the interstitial spaces shall everywhere be continuous with the external wetting phase reservoir and the external non-wetting phase reservoir, respectively. It will become apparent immediately that in any instance when a greater pressure is recorded in the external wetting phase reservoir than in the external non-wetting phase reservoir, one may establish either that static equilibrium has not been attained or that discontinuities in one or more of the fluids have been developed. This is because the pressure otherwiee is always gereatest in the non-wetting phase at each static interstitial interface of contact with the wetting phase. such that the externally measured pressure in the non-wetting phase likewise must be greatest if the above conditions are to be satisfied.

Jan 1, 1949

By A. S. McLatchie, R. A. Hemstock, J. W. Young

Much attention has been given in the past few years to methods of increasing the recovery of oil from proven reserves. Numerous laboratories have made investigations to evaluate the possibilities of increased oil recovery by high-pressure injection of dry gas, injection of a propane slug followed by dry gas, solvent flooding. and by the injection at relatively low pressures of gases enriched with ethane and propane. Several years ago, Whorton and Kie-schnick' published the results of laboratory studies on high-pressure gas injection which showed that, in the case of light oils, recoveries could be considerably increased by sweeping the reservoir with dry gas at pressures in excess of 3,000 psig. The increase was attributed by those authors to the vaporization of oil at the invading gas front and viscosity and solubility effects produced at the front by the invading gas. Later, Stone and Crump' presented the results of a series of displacement experiments in which a light under-saturated crude oil was displaced from sand-packed columns with unusually high recoveries when the displacing gas was a rich condensate or a dry gas enriched with ethane or propane. They also conducted similar experiments at higher pressure on heavy undersa tu rated crude oil, although in this case the increase in recovery was not as great as in the case of the light oils. In both cases, viscosity reduction and swelling of the by-passed oil behind the invading gas front were believed to be responsible for the more favorable recovery of the original oil in place. Within the past year, other investigators", ' have presented the results of laboratory studies of miscible slug and solvent flooding recovery processes. This paper describes the laboratory methods developed for evaluating benefits to be obtained by enriched gas drive in specific reservoirs, and presents the results of several displacements of crude oils which possess a wide range of physical properties. The displacements were conducted at reservoir conditions of temperature and pressure. The apparatus used in the following experiments consisted of a sand-packed tube which served as the model reservoir, a cylinder of injection fluid, and a mercury pump. The stainless steel tube, 8 ft long and 0.53 in. I- was packed with a graded quartz sand. The high-pressure pump discharged mercury into the bottom of the injection fluid cylinder at a constant rate as low as 1 cc/hr. The average porosity and permeability of the sand column were 34.6 per cent and 3.25 darcies, respectively. In each case the tube was charged by the displacement of salt water by the reservoir oil under consideration. Recently a project was initiated to evaluate oil recovery by enriched gas drive from three oil reservoirs. Samples from a fourth reservoir (in this case high-viscosity oil) were studied with a view to obtaining recovery information of general applicability to low-grade, high-viscosity crudes. The oils from these four reservoirs exhibited a wide range of physical properties, and the reservoir conditions of pressure and temperature simulated in the laboratory represented several typical field conditions under which enriched gas drive might be employed. One of the reservoirs selected for laboratory displacement experiments produced an intermediate-gravity crude (29.6" API) by solution gas drive and a weak water drive. A low recovery in the range of 10 to 20 per cent was anticipated. Four displacement experiments were made to determine the effect of injection gas composition and initial gas saturation upon recovery of oil from the laboratory model. Two types of reservoir oil were used in these experiments. In the first run, a desaturated crude with a bubble point of 395 psi was charged to the tube. In the three subsequent runs, a simulated original reservoir oil was charged at 2,000 psi and produced by solution gas drive to 300 psi before beginning gas injec-