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By N. J. Grant, B. C. Giessen, M. Morris

The slvuclures of alloys in the system In-Bi have been investigated after (levy vapid queuching from the mell (splat cooling) to -190°C. Tuo-phase fields could be suppressed over most of the tota1 concentvalion range; five melastable phases a1, a2, ?, ?1. and ß exisl, of which four have simple elementtike structures. For example, ß has the A5 struclure of white till. Crystal-tographic data and coordination numbers for these phases aye given, as well as addilional information on the equilibrium diagram, where a new phase In5Bi3 teas found. THE phase diagrams of binary combinations of B elements from the groups B2, B3, B4, and B5 are usually of a simple type and show considerably fewer intermediate phases than combinations of these elements with A metals, transition metals, or the B1 noble metals. Aside from phases such as the typical B3-B5 compounds with the ZnS-B3 structure type, few stoichiometric phases are known; among them are In2Bi and 1nBi.l Nonstoichiometric phases include ß (In-Sn), a1, (In-Pb), and the tin-rich ? phases in the In-Sn, Cd-Sn, and Hg-Sn systems.' The first two phases have a close relationship to indium, while the latter group are known to be structurally related to a Sn. Thus, there are generally no immediate experimental data for the correlation of the crystal structures of B metals and B metal combinations with certain monotonously varying parameters, such as the valence electron concentration (VEC), or the average atomic size. Such parameters have been recognized as structure determining, e.g., for the transition 4 Sn — y phase,2,3 where nonintegral valence electron concentrations are encountered. It should be possible to extend such correlations to other binary systems, if nonequilibrium single-phase alloys could be produced over broad valence electron concentration ranges, and if their crystal structures could be regarded as being imposed by their electronic states. It has been shown in the case of the tin-rich 7 phases3 that alloy phases with typical crystal structures can be produced in B metal alloys rapidly quenched from the liquid to -190°C by the splat cooling technique due to Duwez,3-8 and reviewed in Refs. 5 and 6. The In-Bi system was selected because it extends over a valence electron concentration range in which several metastable, nonstoichiometrir phases could be expected to occur. Further, the low melting points of the known intermediate phases, In2Bi and InBi, Fig. 1(a), indicated low binding energies and thus possibly low driving forces for the formation Of the equilibrium structures. EXPERIMENTAL TECHNIQUES AND RESULTS The preparation of the quenched foils followed the practice described in Ref. 3. Master alloys were produced by melting of indium (99.97+) and bismuth (99.99+) in evacuated Vycor capsules or in an inert gas arc furnace; quantities of 20 mg were splat-cooled onto copper and silver substrates held at - 190°C; and crystal structures and lattice parameters were determined on a GE XRD-5 diffractometer using Cu Ka, radiation at -190°C and at room temperature. The duplication of each run with both substrates permitted the elimination of overlap of the substrate diffraction pattern and that of the investigated substance. The XRD patterns were usually taken from sin2 " = 0.03 to 0.35; the substrate was used as a means of internal calibration. The fractional accuracy of the lattice parameters of metastable phases is approximately 10-3 In the following, all percentages are in atomic percent. The stable and metastable phases found after rapid quenching to -190°C are listed in Table I, together with estimated concentration ranges and crystallographic data. The investigated alloys and phases present in them are given in Table 11. Except for the region between indium with 33 and 50 pct Bi, where a revision of the equilibrium phase diagram became necessary to include a new stoichiometric phase In5Bi3, the diffraction patterns taken after heating to room temperature agreed with those expected from the phase diagram, Fig. l(a). This suggests that the new nonstoichiometric phases are not stable at room temperature, thus following the observations made for the y phases based on tin.3 Results concerning the equilibrium phases In2Bi and In5Bi3 and the revision of the equilibrium phase diagram which is made necessary by the inclusion of In5Bi3 will be treated first. The Crystal Structure of In2Bi. Makarov7 had identified In2Bi as belonging to the AlB2-C32 type ; however, in a later paper the structure was revised.8 In2Bio was found to be of the Ni21n-B8ß type,21 with a = 5.496A, c = 6.57.9A, and N = 6 atoms per unit cell.9 This crystal structure was confirmed in the present work; definite evidence for the doubling of the c axis, as compared to the A1B2-C32 type, and for the proposed order structure, was found in the powder pattern. The observed lattice parameters agree well with those of Ref. 8; those measured at -190°C are given- in Table I. The Crystal Structure of In5Bi3. A new, equilibrium, intermediate phase was identified in slow-cooled, as-cast alloys; it was identified as In5Bi3. The structure has been worked out by Giessen and Grant;" lattice parameters at -190°C are given in Table I. This phase is probably identical with "In3Bi2", produced by vapor deposition techniques, but not recognized as an equilibrium phase by Palatnik et a1.11 After completion of the present work, the existence of In5Bi3 has also been demonstrated by superconductivity measurements on In-Bi alloys.20

Jan 1, 1968

By R. W. Kraft

A comprehensive analysis of the crystallographic and metallographic structure of several Al-CuAl, lamellar eutectic grains solidified under equilibrium conditions has been performed. A consistent pattern was discovered which was interpreted in terms of a detailed atomistic model of an interface describable as: Interface II {111} AL 11 {211} <101>Al <120> ? Several arguments are presented to substantiate the theory. It is compared in detail with another interface model characteristic of the Wid-manstatten precipitate of CuAl2 in A1 at low Cu levels. In addition, a concept is proposed to help explain the structure of the compound CuAl2. It has been shown that the eutectic alloy between A1 and CuA1, can be forced to solidify as substantially parallel lamellae throughout a relatively large volume&apos; by appropriately controlling the solidification parameters of growth rate, thermal gradients, and impurity level and by causing solidification to proceed in a unidirectional fashion from one end of an ingot to the other. A typical ingot solidified in this manner shows three distinct zones along the length of the ingot, Fig. 1. At the head end is a region consisting of many different grains, some of which are elongated slightly in the direction of solidification. After a few centimeters of growth, this polygrained region gradually merges into the second zone which consists of a very few elongated coarse grains. The third zone at the tail end is a region of eutectic colonies caused by segregation of impurities. Microscopic examination of transverse and longitudinal sections of the ingots reveals that during the initial stages of growth (zone I) the lamellar structure is frequently highly distorted and twisted but that it straightens out in zone 11. This characteristic pattern suggests that nucleation of a eutectic grain begins randomly at the head end of the ingot, and that some particular orientation relationship between the phases is more favorable from an energy consideration than others for one reason or another, so that some grains grow and others which are less favorably oriented do not. The favorably oriented or "low energy" grains continue to grow until excess solute rejected at the advancing liquid-solid interface destroys the parallel lamellar structure by forming a cellular rather than a substantially planar interface. When this occurs, the parallel lamellae fan out and eutectic colonies are formed because the lamellae grow perpendicular to the local interface. Questions naturally arise as to the crystallographic nature of the "low energy" grains. What do the grains which persist into zone II have in common? Can this explain the stability of such grains during growth? To answer the first question it is necessary to determine the crystallographic orientation of the lamellae of each phase relative to one another. This has been done for Al-CuAl2 eutectic alloys by two different techniques on specimens prepared in different ways.2&apos;3 The results were different from each other and from a third orientation relationship between A1 and CuA1, reported for overaged A1-Cu alloys.4 The three orientation relationships are summarized below to illustrate their similarities and their differences. (001) ? 11 (001) A1; [l00] ? 11 [l00] Al Eutectic, Ref. 2 (001) 8 1) (001) A1; [1001 ?11 [1101 A1 Eutectic, Ref. 3 (001) ? 11 (001) A1; [l00] ? 11 [310] Al; Widmanstfitten, Ref. 4 It is not surprising that different orientation relationships were found by Ellwood and Bagley,&apos; and Takahashi3 since the solidification conditions were quite different. Nor is it surprising that Mehl, Barrett, and Rhines 4 found still another value since they were studying another type of alloy. Nevertheless, it would be expected that some logical and systematic pattern could be found if all the alloys were at equilibrium since the same two phases are

Jan 1, 1962

By John C. Sawyer

A brief review is given to show that catastrophic oxidation of stainless steel in the presence of lead oxide is similar in many respects to catastrophic oxidation as caused by MoO3 and V2O5, Experimental data are presented to show that lead oxide accelerates the normal oxidation process of stainless steel by chemically altering the normally protective oxide film formed on the base metal. Data are given to show that similar reactions occur during oxidation of stainless steel in the presence of MOO3,and V2O5. THE mechanism by which pure metals oxidize at high temperatures has been the subject of intensive research for many years and much has been accomplished towards understanding the processes involved. The mechanisms by which alloys oxidize have also been investigated, but due partly to the fewer number of investigations and partly to the complexity of the oxide systems present, available knowledge is not as extensive as with pure metals. When oxidation processes are further complicated by atmospheres contaminated with sulfide, halide, or oxide vapors, the knowledge of fundamentals becomes meager or altogether lacking. Thus, it is not surprising to find that the catastrophic oxidation of stainless steels in metal oxide vapors of MOO, and V2O5 is not a well understood phenomenon despite the fact that a number of investigations have been undertaken. The literature in dealing with the subject of catastrophic oxidation is primarily concerned with the effects of MOO3 and V2O5, but does mention that other metal oxide vapors, one of which is lead oxide, appear to promote a similar type of accelerated oxidation. While this latter effect is virtually unknown, the deleterious effect of lead oxide is of considerable commercial importance, as it is believed to be one of the fundamental reasons for exhaust-valve failure in gasoline engines. For this reason studies have been in progress for many years attempting to better understand the mechanism involved. Modern exhaust-valve alloys"2containing 20 to 25 pct Cr plus nickel and/or manganese are in effect high-grade austenitic stainless steels exhibiting ex- cellent oxidation resistance in air at exhaust valve operating temperatures of 1100° to 1700°F; yet these same alloys are prone to corrode during engine service because of the conditions attending their operation. These conditions are such that the valves become coated with deposits of complex lead compounds mainly derived from gasoline additives of tetraethyllead, ethylene dibromide, and ethylene dichloride. Literature searches3-7 and discussions with various investigators show that considerable difference of opinion exists as to the nature of the lead-bearing deposits found on the surface of exhaust valves and the atmospheres to which they are subjected; yet, all seem to generally agree that corrosion, a gradual transformation of alloy to nonmetallic products of corrosion, is a consequence of the presence of lead compounds. This majority opinion seems to be substantiated by laboratory engine tests which show that corrosion does not occur to any appreciable extent when lead-free fuels are used. The first observations of catastrophic oxidation reported in the literature were probably made by pfeil,8 but it was Leslie and Fontana9 who undertook the first detailed study of the phenomenon. Their work was chiefly centered on the acceleration of oxidation which took place when stainless steels containing more than 3 pct Mo were heated in air with restricted circulation. These investigators reported that the presence of other oxides near the surface would further accelerate the rapid oxidation which occurred. While they recognized that the effect was attributable to the presence of molybdenum, it was Rathenau and Meijering" who emphasized the fact that the presence of molybdenum in the alloy was incidental to the presence of MOO3 vapor in the atmosphere surrounding the specimens. Evans,11 as well as Cunningham and Brasunas 12 studied similar

Jan 1, 1962

By J. D. Sudbury, J. E. Landers, D. A. Shock

The external corrosion of casing is one of the most important problems facing the present day production man. A 1953 NACE report&apos; estimated the annual cost of casing corrosion at $2,200,000 in 22 fields studied. The fields represented only 10 per cent of the wells in the United States. It was significant that 77 per cent of the failures reported were due to external corrosion. A variety of means for combatting the casing corrosion problem have been discussed in papers such as the NACE survey&apos; mentioned previously. No attempt to revicw these will be made in this paper. Thc scope of this paper has been limited to a discussion of the following major items: (I) an instrument for studying external electrolytic corrosion; (2) use of this instrument to determine the quantity of protective current required to prevent corrosion of casing; and (3) problem of accelerated external corrosion of the oil string at the base of the surface string. ELECTROCHEMICAL MECHANISM OF CORROSION It IS gcncrally belleved that one major cause of external corrosion is the existence of electrolytic cells operating between various formation waters. A theoretical discussion of the role of earth potentials in casing corrosion has been presented by L. de Witte and F. J. Radd.2 A brief picture of the electrolytic corrosion action between two differcnt formations (A and B) is presented in Fig. I. This picture is a review to many but is given to insure clarity. In the anode area, oxidation takes place as iron ions go into solution in formation A as a product of corrosion. In the cathode area. reduction takes place and hydrogen atoms are formed at the boundary between the pipe and formation B. The flow of electrons. as indicated. is into the pipe at the anode or corroding area and out of the pipe into the formation at the cathode. In order to conform with regulations of this journal, the flow of a conventional current (I! is also indicated in this sketch. All subsequent references will be to this so-called conventional current flow and will be indicated by the symbol (I). As this action takes place the layer of hydrogen developed on the cathode offers a resistance to the flow of current in the cell. It is said (hat the cathode has been polarized. This polarizing film can be rcmoved by addition of a so-called dcpolarizing agent which reacts with and removes this hydrogen film. Such an agent must be present in ordcr for this corrosion reaction to go at a rate sufficient to cause a severe corrosion problem. The two common depolarizing agents are: (I) oxy-sen. which readily reacts with hydro gen to form water, and (2) certain bacteria which use atomic hydrogen as part of their life process. It is not difficult to explain the presence of these agents. Oxygen may be present in some very shallow formations. Sulfate reducing bacteria are found to exist in nearly any ground where mud pits might be dug. THE CASING POTENTIAl-PROFILE Instrumentation A sketch of the equipment* uscd in determining casing potential profiles is shown in Fig. 2. The tool is run in the hole using a hoist truck with a three-conductor cable. This tool must be run with tubing and rods out of the hole and should be run with the flow line disconnected. By proper choice of electrode size it can be run in any size casing. The electrodes must be run in an open hole or a hole filled with oil. Measurements cannot be made while immersed in water. The tungsten carbide-tipped knives serve as the electrical robes and arc spaced 25 ft apart. The potential difference along a 25-ft section of casing is measured with a potentinmeter to an accuracy of about 5 mv. Current flowing in the pipe can then

Jan 1, 1956

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.&apos; 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.&apos; 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 Henry Leidheiser, Melvin C. Jr. Hobson

The rate of formation of the intermetallic compound, indium antimonide, at the interface between iudium and antimony at 100°C is greatly increased when a composite electrode of indium electrode -posited on antimony is made the cathode in an electrolytic cell. The amount of indium antimonide formed during electrolytic treatment at constant potential appeared to he proportional to the square root of time, but the scatter of the data, particularly at long times, makes it impossible to state this conclzlsi1:ely. The rate constant for the electrochemical synthesis was estimated to he 1.5 x 10-12 sq cm per sec. A similar- set of experiments was conducted in the absence of an applied potential but under otherwise similar conditions. The rate constant lor the thermal synthesis was less than 2 x 10-14 sq cm per, sec, at least two orders of magnitude less than obtained during electrolytic treatment. In a series of electrochemical studies it was observed that intermetallic compounds formed on the surface of polarized electrodes.1&apos;2 The possibility of using this technique for the electrochemical preparation of intermetallic compounds was investigated and subsequently applied to the synthesis of the semiconducting III-V compounds. Gallium antimonide, indium arsenide. indium antimonide, and indium bismuthide were successfully formed by electrodepositing the Group III element from a boiling acid solution onto an electrode made of the Group V element. The following kinetic studies were undertaken on indium antimonide to obtain quantitative information on the rate of formation of this representative III-V compound under a potential gradient. EXPERIMENTAL The electrolytic cell for these experiments was a modified, three-neck, round-bottom, 500-ml distillation flask. Sealed into the side of the flask was a Luggin probe which monitored the surface of the working electrode and extended out of the flask to a small reservoir containing a saturated calomel electrode. The counter electrode was platinum. The three electrodes were connected to a Wenking po-tentiostat which maintained a preselected constant potential near the surface of the working electrode with reference to a saturated calomel electrode. All potentials noted in this paper are with reference to a saturated calomel electrode at 45° ± 5°C. The potential and the current were both monitored using Sargent Model MR recorders. The antimony electrodes were cast in graphite molds to form spheres about 15 mm in diameter with a shank 6 mm in diameter and 10 mm long. A heavy copper wire (12B & S gage) was soldered to this shank. Collodion was applied for protection to the shank and the connecting part of the copper lead. A snug-fitting O-ring was slipped over the shank and the electrode was then fitted into a teflon holder such that only the spherical portion was exposed. The electrode surfaces were cleaned and chemically polished prior to assembly and introduction into the electrolyte by etching in a modified CP-4 solution (50 parts glacial acetic acid, 10 parts concentrated nitric acid, 2 parts 48 pct hydrofluoric acid). The electrolyte was 10-2 M In+3 in 1 MH2So4 and its temperature was held constant by refluxing. The reflux condenser was open to the atmosphere and no temperature correction was made for changes in barometric pressure. The indium concentration in the electrolyte was checked from time to time by the analytical method outlined below for the determination of the amount of indium antimonide formed electrochemically. A schematic of the recorded potential is shown in Fig. 1. At point A the antimony electrode was introduced into the cell and the open-circuit potential recorded. At point B the potentiostat, preset at the desired potential, was switched on. It was switched off at point C and the potential fell to the open-circuit value of the electrodeposited indium. The

Jan 1, 1965

By Blake M. Caldwell, Harrold D. Owen

The continued use of permanent-type, we11 completion Iras pointed LIP the need for more powerful through-tubing perforating equipment. A new expendable shaped charge perforator has been developed in which the charges are run through the tubing in a vertical position and then opened out to a horizontal position when at the desired shooting zone. The performance of this new tool is comparable to that of conventional casing type perforators. This paper describes the new tool and its applications. Performance data in targets rind under various actual well conditions are presented. INTRODUCTION The general acceptance and increasing use of pernianent-type well completion by the oil industry has indicated the need for through-tubing perforating equipment with performance comparable to that of conventional casing type perforators.&apos;.&apos; To achieve the performance desired, a new, expendable, shaped charge perforator has been developed with adequate power for effectively perforating both 51/2-in. and 7-in. casing below tubing. This has been accomplished without resulting severe damage to the casing and can he obtained under extremes of pressure and temperature. The design of this new tool is a radical departure from previous concepts of tubing guns since it was felt that the two major limitations imposed by previous designs severely handicapped performance. The first of these limitations was the restriction imposed upon the length of the charges by the necessary small inside diameter of the carrier. This resulted from the necessity for compromises in designing a hermetically sealed gun small enough to allow free passage through 2-in. tubing, yet with sufficient wall thickness to withstand some minimum pressure. In an effort to overcome this limitation, the charges were in some cases placed at an angle with the axis of the well with resulting loss in effective depth of penetration. The second limitation concerned the extreme distance of the charges from the casing when the gun was fired. An example of the latter situation is demonstrated by the fact that a conventional 13/4-in. tubing gun centralized in 51/2-in., 17-lb casing has a clearance of more than 1-9/16-in. on all sides. This means that a considerable portion of the force from each charge must be expended in penetrating this 1-9/16-in. of well fluid before it even reaches the casing. With the gun centered in 7-in., 23-lb casing, the amount of fluid penetration required of each jet is in excess of 21/4-in. In a situation where the 13/4-in. gun is touching one side of the 51/2-in., 17-lb casing, the jets from the charges on the opposite side have more than 3%-in. of fluid to penetrate. A similar situation in 7-in., 23-lb casing necessitates the penetration of more than 4-9/16-in. of fluid. The penetrating effect of the charges is severely impaired in passing through so much fluid. Under such conditions, there is usually insufficient force left to penetrate the casing. Previous studies have shown the decided disadvantage of having to shoot through such an excessive quantity of well fluid.&apos;.&apos; The problem. then, was how to position large powerful charges close to the casing prior to firing and still manage free passage through 2-in, tubing. The solution appeared to be in some method of folding sealed charge units in an open type, expendable. 13/4-in. carrier for travel through the tubing, and unfolding them upon their arrival at the shooting zone in the casing. It was desired to control the mechanism electrically from the surface through the regular shooting cable, making the release of the charges independent of the physical characteristics of the well, yet with a provision to prevent the gun from firing until the

Jan 1, 1955

By R. M. Fowler, H. L. Hamner

DURING the last 25 years, there appeared in the literature a number of papers describing equipment and operating techniques for the determination of total oxygen in iron and steel. In the early papers, comparatively little attention was paid to side reactions that occur when iron is saturated with carbon at a high temperature in a high vacuum. As more experience was gained with the new method, the limitations appeared. Metals, with a boiling point lower than iron, distilled out of the crucible, condensed in the cooler part of the furnace, and subsequently reacted with carbon monoxide to form oxides and carbon. Aluminum, manganese, and the alkaline earth metals proved troublesome in this respect. Modifications have been devised to overcome the difficulties due to aluminum and manganese, while the alkaline earth metals are not of too much concern as yet to the steel chemist. The reactions of sulphur have received less attention, although it is generally recognized that some carbon disulphide is probably formed. Liquid air traps have been used in some cases to prevent any carbon disulphide from entering the analytical train. Sulphur was not a particular problem at the Union Carbide and Carbon Research Laboratories until the analysis of the irons of higher than usual sulphur contents became necessary. In order to describe the procedure developed for such irons, it will be necessary to first describe the type of vacuum-fusion equipment employed because the operation of vacuum-fusion equipment is an art to a considerable extent. At the Laboratories, vacuum-fusion equipment has been in daily operation since about 1930. Over the years, the evolution of this apparatus has been governed by the versatility required to analyze a wide variety of materials. Since all types of materials from high purity metals to slags are analyzed and, since seldom more than a few samples of one type are analyzed in succession, the apparatus was designed for accuracy and flexibility rather than for speed. A general view of the equipment is shown in Fig. 1, while Fig. 2 shows the relationship of the various parts. In Fig. 2, A is a vertical double-glazed 24X27/8 in. OD silica tube heated with a 20 kva mercury-arc high frequency generator. The tube is closed with a water-cooled brass head attached with de Khotinsky cement. A turret cap fits on this head and is sealed with a 1/8x3 in. "0" ring. The head contains a sight glass and two 8 in. horizontal glass tubes, for sample storage, cemented in with de Khotinsky cement. B is a four-stage Gaede mercury diffusion pump connected to the water-cooled head with a 11/2 in. copper tube through a flange with an "0" ring. The output of the vacuum pump feeds into an automatic Toepler F pump which compresses the gas sample over mercury in the measuring burettes, G and H. There are bypasses in this line for a McLeod gage C and a Piranni gage D, a manometer E, and for initial pumping out of the system with a Cenco Megavac backing-up pump. The reduction crucible shown in Fig. 3 is machined of Tungar Bulb quality (A.G.K.T.E.-2) graphite. The sample is guided into the crucible with the graphite funnel depicted on this figure. The arrangement of the crucible, radiation screens, etc. in the furnace is as follows: A 1 15/16x61/2 in. Alundum thimble, porosity RA-84, with two 1/8 in. holes near the top and opposite each other which take a pair of special tongs used for lowering it in place, is prepared. A 3/4 in. layer of powdered graphite is placed in this Alundum thimble, and the graphite crucible containing 20 g of ingot iron and 0.5 g of carbon is carefully centered on this bed of graphite powder and graphite powder is packed around it to the top of the graphite cru-

Jan 1, 1953

By C. R. Simcoe, T. J. Koppenaal

The effect of direct and alternating currents on the quench aging behavior in an Al-4 pct Cu alloy has been investigated by use of resistivity measurements. The reaction rate increases with direct current density in the investigated range of 1000 to 3000 amps per sq cm. Alternating current of a specific frequency is observed to decrease the reaction rate by a factor of about two. ErDMANN-JESNITZER et al.,1,2 investigated the effect of direct and alternating current on the quench and strain aging behavior of low-carbon iron. In both cases they observed that direct current accelerates the aging reaction and that an alternating current can completely inhibit the aging process. The purpose of the present research was to investigate these phenomena in the quench aging behavior of an Al-4 pct Cu alloy and to determine the correlation, if any, between the increase in the observed reaction rate and possible heating effects accompanying the aging with direct current. EXPERIMENTAL PROCEDURE The aluminum-base alloy used in this investigation contained 3.98 wt pct Cu (1.72 at. pct) with impurities of 0.003 pct Si, 0.002 pct Fe, and 0.001 pct Mg. The alloy was rolled into a ribbon about 0.36 mm thick and 3.7 mm wide. The ribbon was split end from end with the ends being used as electrical contacts and the central unsplit section, about 5.3 cm in length, serving as the specimen. Solution treatment was accomplished by quenching from a salt bath at 520° ± 2°C into water at 25° ±0.5°C; the specimen was immediately transferred to a liquid nitrogen bath. All aging was done at 75° ± 0.2°C in a rapidly stirred ethylene glycol bath. Resistivity measurements were made by the double potentio-metric method employing a standard resistor; for purposes of convenience, the resistance measurements were made at 77°K. The transfer of the specimen from the aging bath to a liquid nitrogen dewar was accomplished in less than 1 sec. The aging kinteics were studied with the specimen being aged under the influence of direct current, alternating current, and without any type of current. The amount of heating caused by direct currents was investigated by soldering a thermocouple on the specimen surface and measuring the temperature change after applying various current densities. The temperature was observed to increase (from 75°C, the aging temperature) about 0.8°, 3.0°, and 8.5°C with direct currents of 1000, 2000, and 3000 amp per sq cm, respectively. When employing alternating current, the circuit was monitored with an oscilloscope and adjustments made to produce a normal sine-wave pattern. RESULTS Prior investigations3&apos;4 in the aging characteristics of A1-4 wt pct Cu have shown that the resistivity initially increases, reaches a maximum, and then decreases to values significantly lower than the as-quenched resistivity. This type of behavior is seen in Fig. 1 which shows the resistivity at 77°K as a function of aging time at 75°C observed in this investigation. At this aging temperature, the resistivity maximum is seen to occur in about 1 to 1-1/2 min and it further decreases to the as-quenched value in about 24 min. The behavior observed with the application of direct currents of 1000, 2000, and 3000 amp per sq cm during aging is shown in Fig. 2. With increasing current densities, (+) ?pmax decreases and the rate of the aging process increases. The time necessary to reach the as-quenched resistivity value decreases from 24 min for aging without current to about 16, 10, and 7 min for aging with 1000, 2000, and 3000 amp per sq cm direct current, respectively. Fig. 3 shows the results obtained when two changes were made during the aging with 2000 amp per sq cm

Jan 1, 1963

By R. D. Pehlke, W. M. Small

The effect of added alloying elements on the solubility of nitrogen in a liquid alloy of 74 wt pct Fe. 18 wt pct Cr, and 8 wt pct Ni has been studied. At 1600°C and 1 atm nitrogen pressure, aluminum, chromium, columbium, manganese, molybdenum, tantalum, and vanadium increase the solubility of nitrogen in the liquid 18 Cr-8 Ni alloy, whereas additions of cobalt, copper, nickel, silicon, tin, and tungsten decrease the solubility. Interaction parameters based on a constant ratio of iron, chromium , and nickel have been used to quantitatively define the changes in nitrogen solubility. INVESTIGATIONS on the solubility of nitrogen in liquid iron have usually treated the pure metal, and often the influence of a single added element. Pehlke and Elliott1 carried out a comprehensive study on the influence of alloying elements on nitrogen solubility in liquid iron, and compared their results with previous studies. Turnock and pehlke2 have recently reported a study on the solubility of nitrogen in multicomponent liquid iron alloys. The original interaction parameter proposed by wagner3 was successfully employed in these studies. The need for obtaining information on the gas solubility in more complex alloys is indicated by the increasingly significant role played by dissolved gases in the processing of iron-based materials. The commercial stainless steels, for example, represent an area where data on nitrogen solubilities are required as a function of composition, temperature, and gas pressure. The nitrogen solubility in liquid Fe-Cr-Ni alloys has been studied by Humbert and Elliott.4 Their investigation covered the entire ternary system, and attempted to use data from binary alloys to predict nitrogen contents in liquid ternary alloys. Langenberg,5 using a method developed by Morris and buehl,6 calculated the nitrogen solubilities in multicomponent iron alloys from data available on binary iron alloys at 1600°C. Nelson,7 using a regular-solution model, extended this prediction to include the effect of temperature. Chipman and corrigan8 and Turnock and pehlke2 also employed empirical methods to calculate nitrogen solubilities in liquid multicomponent iron alloys. In order to provide a basis for predicting nitrogen solubility in liquid stainless steels, and to extend the data available for thermochemically modeling systems of this type, the following investigation was carried out. The study involved measupements of nitrogen solubility in a nondilute alloy and examination of the influence of a small addition of an alloying element on the nitrogen solubility. The study was focused on a very narrow range Of composition in the vicinity of 18 wt pct Cr-8 wt pct Ni (herein referred to as 18-8) with special emphasis on the change of.nitrogen solubility with the addition of a fourth metallic element. EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus, described previously,1,2 was used in this investigation. The charge materials were contained in a recrystallized alumina crucible and inductively melted. Additions were dropped from a glass side-arm. All materials were hydrogen-refined and vacuum-treated to eliminate or minimize the oxygen content. The source and purity of materials is given in Table I. The initial metallic charge was heated to approximately 1000°C and held under vacuum for 30 to 45 min as a means for removing hydrogen and adsorbed gases. Argon was used as the calibrating gas to determine the "hot volume". The average hot volume of the system was approximately 50 cu cm STP and a few experimental runs were made using a reaction bulb with a hot volume of 80 cu cm. The temperature range studied was from 1550° to 1700°C and the temperature was measured optically. THEORETICAL PRINCIPLES General Discussion. Nitrogen dissolves in liquid iron alloys according to the reaction: 1/2N2(g) = N (wt pct in solution) [l] The equilibrium constant, K1, for this reaction is written as:

Jan 1, 1969

By C. Cronquist

Since April, 1962, Shell Oil Co. has operated a peripheral line-drive waterflood of the 10.750-ft lower Tuscaloosa (Cretaceous) Denkman sand in the Little Creek field. Located in southwestern Mississippi in the lower Tuscaloosa trend, the field was discovered by Shell in Jan., 1958. Among the largest in the trend, the accumulation is controlled stratigraphically and occurs in an extensive series of alluvial-point bar deposits across a nose that dips gently to the south. The crude oil is 39" API gravity and was highly undersaturated at initial conditions. Early production behavior indicated a depletion drive with slight water influx; primary recovery wm estimated to be 25 million bbl, or 24.5 percent of stock-tank oil originally in place. A.s a result of a favorable mobility ratio and remarkably uniform rock properties, the volumetric sweep eficiency in the waterflood has exceeded 90 percent. Despite the high connate water saturation (56 percent), the displacement efficiency by water injection has been quite efficient, contrary to traditional concepts. Based on observed field flood-out performance, ultimate recovery is calculated to be 46 million bbl. As anticipated, the production rate began declining during 1964 due to a continu ing reducrion in the number of producing wells as flood fronts advanced across the field. Cumulative recovery as of Jan., 1968, was 44.8 million bbl; waterflood operations ~hould be complete by 1970. Introduction Most waterfloods described in reservoir engineering literature involve pattern operations, the most common of which is the five-spot pattern. Only occasiona&apos;lly are linear drives described, even though there probably are increasing numbers being put into operation. Increasing use of linear floods may reflect the accelerating trend towards early application of fluid-injection programs when linear drives are more efficient, as was the case at Little Creek. However. the Little Creek operation is unusual in several respects. It is one of a few successful waterfloods conducted in sands with connate water saturations approaching 60 percent, and it is among the deepest successful water-floods being operated anywhere. Development The Little Creek field was discovered in Jan., 1958, in the lower Tuscaloosa trend in southwestern Mississippi (Fig. 1). The discovery well, Shell-Lemann No. 1, was drilled on a seismic closure about 2 miles southeast of lower Tuscaloosa production at Sweetwater. The well was completed in the Denkman sand at 10,752 ft, and on initial potential it flowed 588 BOPD of 39" API crude on a %+-in. choke; psi was 730 and GOR was 442:l. Development proceeded rapidly on 40-acre spacing, and by the end of 1958 the field was producing approximately 9,100 B/D from 56 wells. Almost all this production came from the northern half of the field. The southern part was discovered in Nov., 1958, at a location almost 2 miles from previously established production. Subsequent drilling established an apparent conneotion about half a mile wide between the twd areas. Development of the field was practically complete by 1961 with the drilling of 155 producers and 35 dry holes. Some early wells were completed open hole but moslt are completed with casing cemented through the productive interval and perforated for production. Geology The lower Tuscaloosa structure in this area is a north-south nose with maximum dips of about 2" on the flanks. There is no discernible faulting at the producing horizon. Productive limits of the field are shown in Fig. 2, which is contoured on a marker just above the main productive zone. A common water level at 10,415 ft subsea was logged at both the northwest and southeast ends of the field. There is a gross oil column of nearly 100 ft (Fig. 2). Since there is less than 40 ft of closure, it is apparent that bhe accumubtion is controlled stratigraphically, being limited by a sand pinch-out across the creslt of the nose. The total produc-

Jan 1, 1969

By R. E. Cook

This paper presents results of a study to determine to what extent errors in estimated free gas saturation affect the results of static pressure calculations from build-up curves in two-phase systems. Use is made of the method of pressure build-up curve analysis developed by Miller, Dyes and Hutchinson1 , with modifications for two-phase flow advanced by Perrine2. Cornhined fluid compressibility of gas-oil mixtures is included, with special attention given to the discontinuity that occurs in fluid compressibility at the saturation pressure and its effect on static pressure calculations from build-up curves. The sensitivity of static pressure calculations to errors in gas saturation is considered over wide ranges of formation and fluid properties and reservoir pressure conditions. It is concluded from this study that for analyses of two-phase pressure build-up curves (I) the use of under-saturated crude compressibility data, even when producing GOR&apos;s are at or near solution values, will result in very significant negative errors in calculated static pressrrre, and (2) except for large values of buildup curve .slope and/or very low crude gravities, rather large errors in calculated gas saturation can he tolerated without .significant effect on calculated static pressures. The conc1usions arc qualified as referring only to the effects of gas saturation and excludc possible errors in the nuumerous other factors that enter into the ancllysis of pressure build-up curves. INTRODUCTION As part of the analysis of basic data for several major Eocene reservoirs in the Bolivar Coastal field (Western Venezuela), it was necessary to analyze a large number of pressure build-up curves for oil permeability and static reservoir pressure. From performance data it became apparent that gravity segregation is very active in these reservoirs. As a result of this performance it was recognized that the free gas saturation within the oil leg of the reservoirs would be small but would be subject to certain errors in calculation due to the inaccuracy of relative permeability data in the low gas saturation region. Since all of the various methods of build-up curve analysis were originally derived for sin- gle-phase, constant compressibility systems, and since the presence of a small but rather indeterminate gas saturation would greatly affect the reservoir fluid compressibility, a study was undertaken to investigate the effect of gas saturation on the results of two-phase pressure build-up analyses. TWO-PHASE BUILD-UP CURVE ANALYSIS The method of analysis used in this investigation is basically that originally developed by Miller, Dyes and Hutchinson1, with modifications for two-phase flow advanced by Perrine2. Miller, et al, showed that the original equation for single-phase permeability away from the well bore, held for two-phase flow except that the calculated permeability is the effective permeability to oil away from the wellbore. This finding was acknowledged by Per-rine, who also presented the equation for effective gas permeability* as Since Eqs. 1 and 2 contain no terms influenced by fluid compressibility, no distinct problem should develop in calculating permeability from two-phase build-up curves. In regard to the calculation of static reservoir pressure from build-up curves in single-phase systems, the modified Miller, et al, method as presented by Perrine is briefly as follows. 1. From build-up curve data, PVT data for the reservoir fluid and the well spacing and sand thickness, calculate the climensionless shut-in time corresponding to the highest value of actual shut-in time (t, hrs) on the straight-line portion of a semi-log build-up curve. Dimenrsionless shut-in time is related to actual shut-in time by the relation, t- 0.000264 kt 2. From a graph of dimension less shut-in time vs dimensionless pressure difference (Fig. 1 1 ) find the value of dimensionless pressure difference corresponding to the value of 7 calculated under (1) above. Dimen-

By R. Schuhmann

D. W. Fuerstenau (Associate Professor of Metallurgy, Dept. of Mineral Technology, University of California, Berkeley, Calif.) In his excellent paper, Dr. Schuhmann has proposed a mechanism for conlrninution which can be utilized to explain a number of phenomena which have been observed in the size reduction of solids. The difference between the product obtained from a ball mill and from a rod mill can readily be explained by Dr. Schuhmann&apos;s hypothesis. Consider that the size distribution of the product from each comminution event is given by y; - 100 (x/ki) (1) where Yi is the cumulative percent finer than size x, ki is the size modulus, and is the distribution modulus for the single comminution event. The total product from a cornminution operation will be the summation of the products from all of the individual cornrninution events. If the size moduli from the various comminution events range from kl to kn , the size distribution of the total product will be a straight line on a log-log plot only to a particle size equal to k ,. Considering 100 volurnes of feed, the value of y for x equal to kl is Riven by where y is the cumulative percent finer than size kj, z is the number of comminution events of kind i, and vi is the volume of each particle crushed. y=z1 qv1+z2 qv2 (k1/k2) +.............zn qvn (k1/kn) (3) F or particle sizes greater than k1 7 e. 6. x = k3, the value of y will be given by k3 A y = z1 qv1 + z2bv2 + Z3uV3 + zn zn qvn (k3/kn)(4) Only when x is equal to k, will y equal 100. &apos;Thus, the total product from a comminution operation will be a straight line on a log-log plot strictly up to a particle size equal to kl and above that size the line will curve so that y will equal 100 for the coarsest particle or k, (see Fig. 1). The actual shape of the size of distribution curve will depend upon the relative number of conmninution events of different kinds. In the case of ball milling, the ratio kn/kl may be pite large and there will be considerable deviation at the coarse sizes in a Schuhmann plot. kIowever, the grinding action in a rod mill is such that fine particles are protected from the rods by the coarse particles. Consequently, kn/kl will be quite small and the product from a rod mill will give a straight line Schuhmann plot almost to y equal 100%. In his paper, Dr. Schuhmann also has presented a very straightforward definition of grindability derived from the basic energy equation E = Ak-a (5) where E is the energy required to comminute a material to a size modulus of k and A is a constant. According to Dr. Schuhmann, the grindability of a material is the volume of material comminuted finer than unit size per unit of energy expended, this being 1/A. For comparison of grindabilities at any size two numbers are required, both = and 1/A, and anyone tabulating grindabilities should give both of these numbers. Concerning the experimental determination of grindabilities, if the material being comminuted possesses distinct cleavage, the energy re quired for comminution is given by E = Ak-(a-y) (6) where y is small number less than = . Because of cleavage, less energy will be required for comminution. To be certain that cleavage does not affect the gindability of the material being tested, it is suggested that the method used by Dr. Charles for determining grindability be used to ascertain if the deviation exponent y is zero or finite. R. Schuhmann, Jr. (Author&apos;s Reply) Dr. Fuerstenau&apos;s interesting comparison of rod milling and ball milling

Jan 1, 1961

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,&apos; 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 C. G. Dunn, F. Lionetti

The energy associated with grain boundaries in polycrystalline aggregates is believed to play a major role in grain growth processes and, when growth ceases, to determine the final equilibrium grain boundary angles. Further, the energy of grain boundaries of recrystallization nuclei is a factor in nucleation processes. It is important to know, therefore, how the energy per unit area of a grain boundary, that is, the grain boundary surface tension y, depends on the difference in orientation of the two lattices of the grains producing the boundary. Although the problem is important, surprisingly little has been done toward a quantitative evaluation of the effect of orientation difference on grain boundary energies. C. S. Smith1 recently has discussed this problem and in addition to showing effects of orientation difference on equilibrium angles has shown a variety of interesting effects of surface tension on the appearance of microstructures. Fig 1 and the following relations expressed in Eq 1, which connect equilibrium grain boundary angles and surface tensions, illustrate equilibrium conditions which are believed to hold true in metals. ?l2 _ ?23 _ ?l3 [1] sin ?3 sin ?1 sin ?2 Clearly any two of these surface tensions can be expressed in terms of the third when the equilibrium angles ?1, ?2, and ?3 are known. Applied to the present problem for solid state equilibrium of three grains, the angles ?1,?2 and ?3 must be measured in a plane perpendicular to the line of junction of the three grains. Normally a direct determination of these angles from random microsections is impossible. Consequently Harker and Parker2 and Smith1 (except for some measurements on flat specimens) resorted to a statistical method to determine equilibrium grain boundary angles. Smith reported that grain boundaries meet the surface of a piece of metal nearly perpendicularly. He reported also, in connection with direct angle measurements on flat specimens with grains extending through the thickness, that angles varied appreciably from 120" and concluded that there was a measurable effect of orientation difference on surface tension. Another direct way of determining equilibrium angles and a method adaptable to studying particular configurations, recently suggested by Dunn,³ is to use a three-grain flat specimen with orientations of grains so chosen that the junction line of the three grains will be straight throughout the thickness and perpendicular to the surface of the specimen. Choice of orientations is possible when individual grains of each group can be grown to predetermined orientations through the reorienting and growth of " seed crystals " as described.³ Not only is it possible, for example, to have grains with the same crystallographic plane in the plane of the specimen, but a given orientation difference between two grains can be made a common factor to an unlimited number of three-grain groups while a series of orientation differences is investigated. Any effect of anisotropy of gas-solid surface tension due to grain orientation should be minimized by having all gains oriented the same with regard to crystallographic plane in the plane of the specimen. Another feature of the three-grain group is the notched grain boundaries as shown in Fig 2 for one specimen (S4). The notches serve to anchor the end positions of the grain boundaries (especially at high temperatures) while the central and junction point of the grains moves toward an equilibrium position. Final equilibrium should produce straight grain boundaries if the notches are very narrow and if changes in orientation* of the grain boundary do not alter the surface tension.† If one assumes the straight line condition and no change of surface tension with small changes in grain boundary orientation and finds the equilibrium configuration by a minimization of the grain boundary energy, one obtains the relations given in Eq 1. The approach to straight line boundaries or to minimum energy configurations in specimens containing large grains, such as those used in the present investigation, may be very slow compared with the approach to equilibrium conditions for the grain boundary angles. It may be desirable, as proved to be the case in the present investiga-

Jan 1, 1950

By R. T. Hukki, P. Voutilainen

This paper describes a new apparatus for continuous wet fine-screening. Its preferred size range seems to be from 0.1 to 1 mm. The supercritical trommel screen is a short cylindrical trommel of wedge-bar type construction operated at a speed greater than the calculated theoretical critical speed and at a speed lower than the speed at which particles introduced into it will centrifuge. The paper describes results obtained with the prototype supercritical trommel screen in pilot plant scale. The results point to a high capacity and simultaneously to a high sharpness of screening. Finally, an analysis is presented of the forces acting in screening on a supercritical trommel screen. In the era of high speed, high capacity processing of raw materials the conventional slowly rotating trommel screen is often considered a relic from the times passed. A typical trommel screen is the cylindrical trommel rotated about a horizontal or slanting axis at a relatively low speed. Its screening characteristics are well known. Trommel screens of various types of construction, methods of operation, performances and other characteristics have been described in detail by Taggart.1 The theoretical critical speed of a trommel screen is defined by the same well known equation as that applied for grinding mills: where ncritical = the numerical value of the theoretical critical speed in rpm, D 1 = the inside diameter of the trommel in feet, and D2 = the inside diameter of the trommel in meters. ncritical corresponds also to the centrifuging speed provided that the coefficient of friction f between the trommel surface and the outer layer of the charge is = 1.0. In a general case: From Eq. 2 it is seen that in all cases where f < 1.0 the centrifuging speed of the trommel is greater than the theoretical critical speed. The supercritical trommel screen concerns screening operations within that speed range which is between the theoretical critical speed defined by Eq. 1 and the centrifuging speed defined by Eq. 2, under conditions such that the coefficient of friction f<1.0. It is reported by Taggartl that the optimum speed of a conventional cylindrical trommel screen 36 in. in diam was experimentally found to be about 16 rpm. From Eq. 1, the critical speed of this trommel is 44.2 tpm. The indicated optimum speed corresponds to (16/44.2) x 100% = 36.2% of the theoretical critical speed. The optimum speed range based on information available seems to vary from 33% up to 45% of the theoretical critical value. The trommel screen operated at a supercritical speed: operates at a speed greater than the calculated theoretical critical speed; operates at a speed lower than the speed at which the charge introduced into it will centrifuge; operates within the supercritical speed range in such a way that the coarse fraction of the charge must slide in respect to the inside surface of the trommel; the outer layer of the said fraction next to the screen tends to proceed in the same direction as any selected point on the trommel surface, but now at a lower speed, and indeed at a subcritical speed; allows to a certain degree adjustment of the maximum determining particle size x of the fine product simply by a variation of the speed of the trommel within the supercritical speed range. With increasing trommel speed, finer and finer material only will get the opportunity to find its way into the fine product while the screen opening remains constant. In conventional practice, the low speed trommel is generally used for sizing of coarse and medium coarse material, but seldom for fine screening. The characteristic feature of the product passed through the conventional trommel is that the determining size x of the biggest particle is barely smaller than the nominal size of screen opening. The supercritical trommel screen, on the other hand, is best suited for sizing of relatively fine material. Furthermore, the characteristic determining size x of the biggest particle in the fine product can be substantially smaller than the nominal width of the screen opening or slot. In the trommel screen best suited for the applications

Jan 1, 1965

By Paul A. Farrar, Sanford Adler

The Tz-Zr system was reinvestigated using both metallographic and X-ray diffraction techniques. It mas found that titanium and zirconium are soluble in all proportions in both the a and 0 phases. The minimum in the transformation was found at 50 at. pct and 535°C. THE Ti-Zr system has previously been the subject of several investigations.1-6 A study by Hayes et al.5 using magnesium-reduced titanium and zirconium melted in graphite crucibles indicated that the system was a continuous series of solid solutions in both a and 0 phases with a minimum at approximately 545°C and 65 pct* Zr. These conclusions were substantiated by the work of Duwez4 as well as by the limited data of Craighead et al.,3 Fast,2 and deBoer.1 However, a more recent investigation of the titanium-rich region by Ence and Margolin6 indicated that the solubility of zirconium in a, titanium at 500°C is approximately 22 pct with the a + 0 field extending to approximately 47 pct Zr. Therefore in order to resolve this discrepancy the following investigation was initiated. EXPERIMENTAL PROCEDURES The alloys used in this investigation were prepared as 20- to 30-g buttons by nonconsumable electrode melting in a helium atmosphere. The starting materials were Bureau of Mines titanium BHN 71 and Foot Mineral iodide crystal bar zirconium. The titanium was premelted before the alloys were prepared to avoid excessive weight losses in the final melting. The compositions of the alloys prepared were as follows: Ti-12.0, 22.2, 29.0, 39.6, 50.0, 58.0, 72.4, 83.5. and 90.8 pct Zr. Prior to heat treatment the alloys were cold-worked 10 to 20 pct, stopping at the first signs of cracking. Specimens for heat treatment were wrapped in molybdenum sheet and annealed in argon-filled quartz capsules for the following times and temperatures: 750°C-40 days, 675°C-61 days, 600°C—109 days, 575°C-112 days, 550°C-112 days, 525°C—127 days, and 450°C —153 days. Quenching was accomplished by breaking the capsules in an iced-brine solution. The standard techniques used for polishing the specimens involved belt grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch7 or "R" etch 8 Debye-Scherrer X-ray powder photograms were obtained for a number of samples using a 114.6-mm camera and CuK, radiation. Exposure times were from 19 to 23 hr. The powder samples were obtained by filing to 270 mesh size. After filing the samples were wrapped in molybdenum foil capsuled in quartz and reannealed at the temperature of original heat treatments; following the heat treatment the samples were quenched into iced brine without breaking the capsules. RESULTS AND CONCLUSIONS On the basis of the microstructural examinations of the heat-treated samples and of the X-ray diffraction data, the Ti-Zr system shown in Fig. 1 was constructed. The data indicate that a, and 0 titanium form a complete series of solid solutions with a, and ß zirconium. The minimum was found to occur at 65 pct (50 at. pct) Zr and 535°C, in excellent agreement with the earlier investigations,1-5 see Fig. 2. Typical microstructures are shown in Figs. 3 to 7. Figs. 3, 4, and 5 show the 22.2, 39.6, and 50.0 pct Zr alloys after heat treatment at 675°C for 61 days with the 22.2 pct Zr showing equiaxed a, and the 39.6 pct Zr alloy a + transformed ß, while the 50 pct Zr alloy shows only transformed B. Figs. 6 and 7 show the 29.0 and 39.6 pct Zr alloys after heat treatment for 109 days at 600°C. The 29 pct Zr alloy has an equiaxed a structure while the 39.6 pct alloy has a partially recrystallized a+ß structure. X-ray diffraction data obtained from the 50 pct Zr alloys after heat treatment at 525° and 450°C as well as from the as-cold-rolled material showed only those lineos which couid be indexed a: a titanium, good agreement with the previously published values. 2,4,5,9 Chemical analysis* of the 50 pct Zr alloy

Jan 1, 1967

By H. H. Podgurski, F. N. Davis

In silver alloys containing less than 0.2 wt pet Cu. the reaction 9 + 1/2 0, = CuO(s) was found to proceed to equilibrium between 700o and 808oC. From measurements of the equilibrium dissociation pressures of the CuO at several temperatures, the differential heat of solution and the activity coeflicients for copper in silver were calculated. These values were found to be in reasonable agreement with those calculated from data appearing in the literature. A metastable "copper oxide" with an atom ratio of oxygen to copper as high as 1.7 was formed by internal oxidation at 300°C of these same dilute Ag-Cu alloys. No anomalous behavior was noted in the temperature dependence of oxygen solubility in silver. The solubility minima between 300" and 800°C reported several years ago can be accounted for, at least in part, by reactions with trace impurities, such as copper. Cold-worked siloer exhibits an enhanced permeability to oxygen. THIS investigation was undertaken because of our interest in interactions between solute and lattice defects in metals. The reason for the choice of the O-Ag system for study is the anomaly in the solubility of oxygen in silver reported by Steacie and Johnson1 in 1926, specifically that isobars between 100 and 800 Torr show solubility minima at 400°C. It was also claimed that the copper impurity in the silver was not responsible for the minima. Recently, Eichenauer and Müller2 proposed that surface adsorption might have been responsible for this solubility anomaly, but no adsorption isotherms are available to check the pressure and temperature dependence observed at the low temperatures. Surface-tension measurements on silver made by Buttner, Funk, and udin3 suggest that a considerable fraction of a monolayer of oxygen exists on silver at 922°C and at an oxygen pressure of 150 Torr. To account for the pressure sensitivity reported by Steacie and Johnson1 at 300°C, the oxygen bound to the surface at 922°C cannot be considered relevant; the existence of a surface layer at 300°C characterized by a lower energy of binding would be required to explain the effect. All of our attempts to detect an interaction of this type with surface sites have failed. In this investigation we have not been able to associate the dissolution of oxygen in silver with a dislocation interaction. Evidently, severely cold-worked silver does not contain a sufficient number of trapping -sites for oxygen. Indeed, our work shows that oxidation of trace impurities in the silver was probably responsible for Steacie and Johnson&apos;s results. In addition, we have been able to establish the nature of the reaction with copper impurity in silver by thermodynamic considerations. EXPERIMENTAL PROCEDURE Measurements of both the internal oxidation rates and the solubility were made volumetric ally in a system equipped with a gas burette, a mercury manometer, a McLeod Gage, and a mass spectrometer. The silver and the silver-alloy samples were protected from contamination by mercury vapor from our pressure gages by suitably placed refrigerated (-78°C) traps. Silica reaction vessels were employed for experiments performed above 500°C. Spectroscopically pure gases were used in this investigation. The highest-purity silver used in the solubility measurements was 99.999 pet. By chemical analysis 2 ppm of Cu were found in this silver. The two Ag-Cu alloys used in this research were made up to 0.14 and 0.15 wt pet Cu starting with 99.999 pet Ag. An unexpected source of error was discovered in the course of the work. At temperatures near 800°C silver distilled from the hot silica reaction tubes into cooler regions of our system. Although the weight loss of silver from the sample was not important in itself, oxygen was being consumed by the silver distilled into the cooler part of the system to form a stable oxide phase from which the oxygen was not recovered. In a separate experiment conducted to determine the necessary correction, losses between 0.2 and 0.3 cu cm (stp) of 0, in 24 hr were measured at 810°C. On the assumption that the flux of silver from the vessel to form Ag2O de-

Jan 1, 1964

By John C. Shyne, Eric R. Morgan

BORON as a hardenability agent of commercial importance has been the subject of extensive study in recent years. It has been suggested in the past that boron increases hardenability by combining with nitrogen, thus rendering it innocuous.&apos; More recently it has been proposed that boron increases hardenability by reducing the free energy of sites of ferrite and pearlite nucleation.&apos; The segregation of boron to grain boundaries, the primary site of nucleation, would account for the large hardenability effect of minute additions of boron in steel. This grain boundary theory has found general acceptance while the concept of boron as a nitrogen scavenger has been disregarded. However, the interaction of boron and nitrogen in steel is considered to be important to hardenability because boron may be made ineffective by combination with nitrogen.". * The present work was undertaken to examine some of the effects of boron and nitrogen arid their interaction in steel. A base composition of moderate hardenability was chosen. This was a 0.35 pct C steel containing 2.50 pct Ni and 0.30 Mo. This composition was used because it contained no strong carbide, nitride, or Table I. Composition of Steels by Analysis, Wt Pct Steel C Ni Mo 0&apos; B N* Base 0.35 2.50 0.30 0.0012 nil <0.0001 Boron 0.35 2.50 0.32 0.0012 0.0022 <0.0001 Nitrogen 0.33 2.60 0.35 0.0015 nll 0.0052 Boron plus nitrogen 0.35 2.48 0.30 0.0006 0.0020 0.0040 * Obtained by vacuum fusion technique. boride-forming elements. The other alloys examined were modifications of the base composition and contained nitrogen, boron, or nitrogen plus boron. The compositions of the four alloys used are listed in Table I. The alloys were vacuum melted from electrolytic iron, electrolytic nickel, ferromolybdenum, and fer-roboron. When required, nitrogen was added by admitting a partial pressure of nitrogen over the melt after vacuum melting. The alloys were cast into 21h-in. diam ingots and hot rolled to %-in. sq bars. No ingot pattern was discernible on the polished and etched cross sections of the hot-rolled bars. The alloys were normalized at 1650°F, then machined into standard %-in. diam end-quench hardenability test bars. Four different austenitizing treatments were used: 60 rnin at 1550°F, 45 rnin at 1800°F, 30 rnin at 2000°F, and 20 rnin at 2000°F followed immediately by 30 rnin at 1550°F. The 1550" and 2000°F treatments were carried out in duplicate for each of the four steels. In order to prevent surface oxidation the bars were austenitized while buried under charcoal in an atmosphere of argon. After quenching the bars in a conventional end-quench fixture, the hardness surveys were made in the usual fashion on parallel flats ground along opposite sides of each bar. These were ground 0.050 in. deep rather than the conventional 0.015 in., to avoid decarburized or deboronized regions.5 The austenite grain sizes which resulted from each heat treatment were observed metallographically using Vilella&apos;s etch for martensite. The criterion used as a measure of hardenability was the distance from the quenched ends of the bars at which a hardness of RC 35 was observed. This hardness represented the inflection point on the hardness vs distance plot. Fig. 1 shows the hardenability of each steel after the several heat treatments. The duplicate tests demonstrated excellent reproducibility; the distance to Rc 35 was reproduced within 1/16 in. for duplicate test bars. All four alloys had the same grain-coarsening characteristics. Neither boron nor nitrogen had any observable effect on grain size. The grain sizes resulting from the various austenitizing treatments were ASTM 7 at 1550°F, ASTM 4 at 1800°F, and ASTM 2 at 2000°F. The small amount of boron in the boron steel greatly enhanced hardenability when the samples were austenitized at 1550°F. The low hardenability of the boron plus nitrogen steel showed that nitrogen eliminated the boron contribution to hardenability. Both steels containing nitrogen, with and without boron, exhibited lower hardenability than the base composition when quenched from 1550°F.

Jan 1, 1958

By F. Forward, H. Veltman, A. Vizsolyi

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963