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By V. Kondic, W. M. Rumball

HUNT and Jackson' have recently suggested that binary eutectics might be classified according to the entropy of fusion of the component phases. Such a classification was in fact proposed2 some time ago by the authors and the purpose of this communication is to present some supporting evidence. As pointed out by Hunt and Jackson' typical metals of low entropy of fusion, ?S, tend to form normal eutectics (using Scheil's terminology3). Where one phase is metallic (low ?S) and the other nonmetallic (high AS) then anomalous structures are formed. These anomalous structures may either be regular (e.g., Bi-Sn)or irregular (e.g., A1-Si). Finally Hunt and Jackson suggest that where both phases are of high ?S regular faceted structures are formed. In the proposed classification2 the ratio of the entropies of fusion is taken as the quantitative parameter, i.e., ?Sa/?SB = E, where e > 1.0. An extensive literature survey has been carried out2,4 for reliable photomicrographs of eutectic structures. The structures, numbering 151, have been classified into two classes, viz., normal (i.e., lamellar and rodlike) and anomalous. The latter group has been arbitrarily subdivided into regular and irregular anomalous eutectics. Details and sources of the structures are given elsewhere.2,4 In the absence of better thermodynamic data the value of E has been determined for each of the systems making the following assumptions and approximations: l) The entropy of fusion of solid solutions may be calculated additively;5 ii) Inter metallic compounds are treated similarly but with the addition of the following term for fully ordered structures.5 -4.573(Ni lOg10 Nl + N2 log10 N2) where Nl and N2 are the atomic fractions. It might be argued that the entropies of fusion are meaningless as the eutectic phases form at some temperature (T,°K) below their true melting point (Ta or Tb). As AS, = Lo/To if La the latent heat of fusion of a, is assumed independent of temperature, the actual entropy change AS& is given by La/Te. The ratio of entropies of fusion then becomes Fig. 1 shows E' plotted against cumulative totals for normal and anomalous systems from which it is seen that normal eutectics predominate at low values of E'; e.g., some 90 pct of normal systems lie below E' = 1.5 with 65 pct of anomalous systems above this value. Fig. 1 also shows that the regular anomalous structures occur mostly at low values of c' possibly suggesting growth more akin to normal than anomalous growth. The choice of c as a classification parameter was based on nucleation concepts, it being observed that metals widely separated in Sundquist and Mondolfo's8 nucleation series were anomalous and those close together normal. The basis of these classification views is really outside the intended scope of this communication but it is hoped to explain them fully in the near future.7 Having arrived at this entropy of fusion classification by nucleation considerations it is interesting to note that Hunt and Jackson's ideas are based on growth considerations. Elsewhere one of the authors4 has shown that an even better classification of the metallographic structures reviewed is obtained from purely conventional heterogeneous nucleation concepts. It has been found that systems having a value of the parameter +b less than 0.28 are almost certainly normal and above this anomalous: V, is the gram atomic volume. This parameter is nevertheless closely related to c and c', these being an approximation of p. The parameter is also related to the other classification3,8,9 which have met with any success in the past. All these classifications are to be reviewed shortly by the authorsU7 A significant thing about the classifications based on

Jan 1, 1968

By H. J. McQueen, G. C. Kuczynski

ThE useful properties of k6-Alfenol and the thermenol alloys (summarized by J. E. Nachman and W. J. Buehler') have encouraged research into those alloys which, having compositions near 25 at. pct Al, 75 at. pct Fe, undergo an ordering transformation between 500° and 550°C. The equilibrium diagram of the iron-rich iron-aluminum alloys was first determined by Bradley and Jay.2,3 They distinguished three structures: the disordered, which is bcc; FeAl, which is simple cubic with one Fe atom and one Al atom per lattice site; and Fe3Al, which is fcc with three Fe atoms and one Al atom per lattice site. This last structure may be conceived as eight body-centered cubes with Al atoms at the centers of alternate ones, so that Al atoms have only Fe as first and second nearest neighbors. Later, Osawa and Murata4 determined the boundaries of the different superlattice regions in the iron-rich Fe-Al solid solution by dilatometric and X-ray methods. Two of the six phases, which they found between 0 and 50 at. pct Al, were never identified by other workers. A. Taylor and R. M. ones,' concurrently with and independently of this research, redetermined this diagram by measuring lattice parameters at temperature. Further reference will be made to their results. EQUILIBRIUM DIAGRAM A) Experimental Procedure—The alloys were prepared from NRC gas-free iron (99.9 pct Fe) and 99.99 pct Al. They were melted in alumina' crucubles under vacuum in an induction furnace. If the ingots were unsound or showed more than a 3 pct weight loss, they were rejected. The ingots were homogenized at 1100°C for 24 hr before hot-rolling at 700" to 900°C from 1 in. to 0.25 in. thick. It is interesting to note that alloys containing more than 28 at. pct Al were able to take an 80 pct reduction of area in the ordered FeAl region. The dilatometer specimens and specimens for chemical analysis were cut from these plates. A Leitz dilatometer was used to measure the coefficient of linear expansion as a function of temperature. The specimens were slowly cooled from 900" to 300°C where they were annealed for 10 hr before slowly cooling to room temperature. The expansion was recorded photographically as the alloys were heated and cooled at 1.5oC per min between 100" and 1000°C. The magnetic measurements determining the Curie points were performed on the dilatometer specimens in the dilatometer, by using direct current in the furnace windings both to heat the specimen at 1.5°C per min and to serve as the primary coil. The regular specimen holder was replaced by a thin alundum tube on which was wound, as a secondary, a closely spaced coil of fine copper wire. A reversal of current in the furnace windings produced, in the secondary, an emf which was proportional to the induction in the specimen, and which could be detected on a galvanometer. In this way, it was possible to determine the Curie points of alloys to within * 5°C. B) Results and Discussion—The coefficients of linear expansion, as obtained from the dilatometer curves, are plotted as a function of temperature and composition in Fig. 1. Since in many cases the heating and cooling curves were superimposed, it was decided to measure slopes of heating curves only. Definite high peaks, due to the transformations, were observed on each curve between 400" and 520°C, and, for alloys containing more than 23 at. pct Al, a second set of smaller peaks at temperatures above 660°C. The sharpness of the peaks indicates that ordering to Fe3Al is a first-order reaction. The compositions and the temperatures of these peaks are listed in Table I. When these temperatures are plotted as a function of the composition, the result is the constitution diagram presented in

Jan 1, 1960

By E. S. Machlin, C. W. Chen

RECENTLY Chen and Machlin' proposed a mechanism for intercrystalline cracking in metals during high-temperature stressing. According to this mechanism the formation of voids at grain boundaries is primarily responsible for intercrystalline cracking. A model has been provided to demonstrate the initiation of submicroscopic cracks and voids at jogs of grain boundaries where grain boundary sliding is inhibited. Submicroscopic cracks can grow as a result of either further grain boundary sliding or localized tensile stress. In the former case, it is believed that grain boundary sliding produces more voids which link together to produce macroscopic cracks and which may lead to the eventual failure of the metal. Concurrently, Nield and Quarrell2 reported their interesting results obtained in a systematic investigation of intercrystalline cracking in two aluminum alloys under various creep conditions. Their observations are generally in agreement with the above mechanism, especially the conclusion that voids are formed as a direct consequence of grain boundary sliding. On the basis of the volume fraction occupied by voids, they could find no confirmation of vacancy condensation as the mechanism for void growth. Furthermore, an important feature of intercrystalline cracking has been likewise pointed out by them that the majority of cracks are not formed at grain corners. Nield and Quarrel1 meanwhile emphasized the importance of grain boundary migration by designating it as one of two main processes operative in the mechanism of crack formation during creep. The designation seems unnecessary because overemphasis of grain boundary migration only complicates the mechanism of void formation. There are two reasons which militate against the inclusion of grain boundary migration in the mechanism of void formation. In the first place, the formation of intercrystalline voids per se does not require grain boundary migration. Secondly, in addition to grain boundary migration, void formation may be minimized by any other process such as plastic deformation which is capable of relieving localized stresses around jogs. Chang and Grant3 have shown that intercrystalline cracking is prevented in aluminum by lattice bending in high stress regions. The influential role played by grain boundary migration in creep has also been realized in our studies. In several cases, voids did not appear at all in grain boundaries whenever grain boundary migration took place prominently during creep. The purpose of this paper is to discuss the effect of grain boundary migration on the formation of intercrystalline voids and other related rupture properties. Experimental evidence indicates that in an unstable grain structure void formation may be markedly modified by structural changes. The abnormally high ductility and the transcrystalline mode of fracture observed in copper at elevated temperatures reveals that effective grain boundary migration minimizes void formation. Grain boundary migration has long been known as a common high-temperature phenomenon in metals with the grain configuration in a nonequilibrium state. Its effect on ductility and mode of fracture has not been recognized until recently.4 Since the introduction of the term "Equicohesive Temperature," the conventional belief has been that below the equicohesive temperature the ductility of metals increases moderately with decreasing temperature until the ductile-to-brittle transition temperature of fracture is reached. In this temperature range, metals fracture in a ductile mode with a "cup-and-cone" fracture surface. Above the equicohesive temperature, ductility remains invariably low and decreases slightly with increasing temperature. The mode of fracture is strictly brittle and intercrystalline. Typical examples have been shown for a brass and copper in Fig. 1 and 9, respectively, in the paper by Greenwood, Miller, and Suiter.5 The observation in the upper temperature range that ductility of metals is low and insensitive to temperature may be explained in terms of void formation at grain boundaries. It is also in accordance with the findings of McLean6 and Fazen, Sherby, and Dorn7

Jan 1, 1961

By P. K. Foh, C. G. Dunn

IN an investigation of the rolling and recrystalliz-ing textures obtained from single crystals of Si-Fe, Koh and Dunn included specimens in the (111) [lie] orientation.1,2 This note reports some additional results obtained on samples of this orientation set aside for further study. After, primary recrystallization longer annealing treatments at 980°C produced only normal grain growth; after 16 hr at 980°C the largest grains were approximately 0.010 to 0.020 in. in diam. The orientations of 13 of the larger grains were found by the transmission Laue method. The unidentified (110) poles of these grains have been added to the (110) pole figure obtained after primary recrystallization2 to give the plot shown in Fig. 1. When grain identifications are also included, such a plot reveals the following. Two orientations agree almost exactly with the peak pole ,density positions of component B of the primary recrystallization texture, one with component A, and one with component C. All the remaining orientations except one have (110) poles near weaker and unidentified pole density peaks. In fact, the correlation is good enough for an identification of eight components. Previously only components A, B, and C were certain. The results are perhaps even more informative when combined with the (110) pole figure of the cold-rolled crystal to give the plot shown in Fig. 2. Each of the 13 orientations is identified and uniquely determined by selecting two (110) poles per crystal, which are 90" apart. The plot shows that every grain of the 13, except grain 6, has a (110) pole in common with a (110) pole concentration of the cold-rolled crystal. The orientation relationship with the cold-rolled orientation may be expressed as approximately 25" rotations about <110> axes, which is in agreement with the results found for coarse-grained primary recrystallization.2 If primary recrystallization had occurred according to the <110> rule without preference, there would have been 12 components. Actually our limited data reveals nine of the possible 12. The integrated pole figure also shows preferences among them, since three are considerably stronger than the rest. In addition to the above direct information, the following conclusions may be drawn. Primary recrystallization of the (111) [110] cold-rolled crystal produces a limited number of weak and strong components with the larger than average primary grains from these components related to the cold-rolled crystal by 25° <110> relationships. In arriving at this conclusion of limited orientations the (111) [110] orientation has to be ruled out as a source of large primaries for two reasons. First, growth in this orientation was not observed, despite an expected high grain boundary mobility (due to its 25" <110> relationship with every component of the texture). Secondly, primary recrystallization usually produces grains in new orientations, particularly in a single orientation matrix; but (111) [110] is not new. Other orientations besides those of the <110> type may be considered unlikely, of course, because the <110> relationship holds quite well for primary recrystallization2 and should produce the large primaries. There are exceptions to this rule, but probably not enough to provide large

Jan 1, 1958

By G. R. St. Pierre, S. W. Gilby

The equilibrium vapors established over Fe-Cr-Ni alloys containing up to 50 pct Cr at 1600°C were determined by collecting the effusate from thoria Knud-sen cells. From these data, the activities of iron and nickel in the ternary alloys have been calculated. In a separate set of measurements, a mass spectrometer was used to determine the activities of the three components in a series of Fe-Cr-Ni alloys. In binary Ni-Cr melts, the activity coefficient of chromium referred to pure solid chromium as standard state is less than one at low chromium contents but is greater than one for melts containing more than 30 at. pct Cr. For Ni-Cr melts containing less than 10 at. pct Cr, In ?Cr = 0.15-0.92 N2. Ternary activity diagrams for Fe-Cr-Ni alloys are presented. In iron-rich alloys, the interactions between the three components are negligible; however, in nickel-rich alloys, the three principal interactions have significant positive values. THE activities of components in binary Fe-Ni alloys have been measured both in the solid solution1-3 and liquid solution4-6 temperature ranges. The determination for Fe-Ni melts have been made by three different methods: transpiration,4 Knudsen-cell effusion with analysis of an accumulated condensate,&apos; and Knudsen-cell effusion with direct measurements of relative component intensities by mass spectrometric methods.6 The results obtained by the three different methods in three different laboratories are in excellent agreement and considerable confidence is placed in the activity coefficients for Fe-Ni melts. At 1600°C, the activity coefficients in dilute solution are ?°Ni = 0.66 and ?oFe = 0.40 for the pure liquid components as standard states. Measurements made on solid solution Fe-Cr alloys7-10 indicate that the component activities are slightly greater than ideal. The measured activities in iron-rich Fe-Cr liquid alloy11-16 indicate almost ideal behavior for this system. The recommended activity coefficient of chromium in dilute solution in liquid iron at 1600o C, ?oCr, is 1.18 when referred to pure solid chromium as standard state and 1.04 when referred to pure undercooled liquid chromium as standard state." The conversion factor of 1.14 is based on a melting point of 1857°C and an enthalpy of melting of 4047 cal per g at. for chromium.21,37 The activity coefficient of iron in dilute solution in liquid chromium has not been measured. Activity measurements on solid Ni-Cr alloys have been made by several investigators.17-20 During the review of this manuscript, Fruehan12 published the results of a study on liquid Ni-Cr alloys at 1600°C. He used galvanic cells22 with ZrO2(CaO) as the electrolyte and Cr/Cr2O3 for the reference electrode. His results indicate that ?oCr in nickel at 1600°C is about 1.01 when referred to pure solid chromium and about 0.89 when referred to pure undercooled liquid chromium as standard state. The activity coefficient of nickel in liquid chromium is unknown. The compositions of vapors freely evaporating from some molten Fe-Cr-Ni alloys have been measured by Lyubimov, Granovskaya, and Berenstein.23 Their results, combined with known vapor pressures, indicate strong positive deviation for chromium in iron-rich alloys and strong negative deviation for chromium in nickel-rich alloys. EXPERIMENTAL PROCEDURES This research was undertaken to determine the activities of components in ternary Fe-Cr-Ni melts containing up to 50 at. pct Cr. At the initiation of the research, we decided to use a Knudsen-cell method wherein a portion of the effusing vapor is condensed on a cold plate.&apos; The composition of the equilibrium vapor for each alloy composition is determined in this method by holding the system under constant conditions for a period of time sufficient to collect enough condensate on the cold plate for chemical analysis. The activities of components in ternary alloys can be calculated from such vapor composition determinations by Eq. [1].24

Jan 1, 1970

By C. E. Berry

Natural stone or manufactured porcelain pebbles are used as the grinding elements in pebble mills and the mills are lined with stone or porcelain blocks. Steel balls usually form the grinding medium in ball mills, and the mills may be lined with steel. Pebble mills are used to avoid contamination by metal of the material being ground, to avoid rapid wear due to corrosion, and for other specialized reasons. Belgian silex (silica) blocks formerly were used widely for lining pebble mills, because of their good resistance to wear, light color, and low cost, but the importation of these blocks was suspended early in the war. The stocks of Belgian silex diminished so rapidly that it was found desirable to compare the properties of a number of domestic substitutes for use in critical operations. Accordingly, a study was made to determine the best substitutes for fine grinding of white pigment and for certain heavy-chemical process work such as the disintegration of phosphate rock in weak phosphoric acid solution. A comprehensive survey of substitute lining materials was not contemplated. It was stipulated at the beginning of the investigation that only materials on the market, available in large quantities, would be tested and that these should be reasonable substitutes from a a ance viewpoint as determined from known physical characteristics. Marble and limestone, for example, could be eliminated immediately. Quartzite, granite and porcelain were selected as likely substitutes for Belgian silex and were subjected to quality tests. Materials Tested 1. Belgian Si1ex.—Sample blocks of a standard grade were taken from crates in which they had been imported. The stone was light gray in color and contained inclusions of small clusters of quartz crystals as well as light colored portions that might be calcite. This was a siliceous rock which appeared to be of igneous origin. 2. Quartzite.—Samples of quartzite were obtained from a quarry in Minnesota. The blocks exhibited a crystalline fracture. The stone was pink in color and composed of fine quartz crystals bound together with a siliceous cement. 3. Granite A was a fine-grained granite quarried in South Carolina. 4. Granite B was coarse-grained granite quarried in South Carolina. 5. Granite C was a coarse-grained granite quarried in North Carolina. 6. Porcelain A.—Sample blocks of the pebble-mill lining material were obtained direct from the manufacturer. It was white in color and of lower specific gravity than the natural materials. It did not have a crystalline structure. 7. Porcelain B.—Sample pebble-mill lining blocks of the porcelain were received direct from the manufacturer. It was white

Jan 1, 1948

By C. E. Berry

Natural stone or manufactured porcelain pebbles are used as the grinding elements in pebble mills and the mills are lined with stone or porcelain blocks. Steel balls usually form the grinding medium in ball mills, and the mills may be lined with steel. Pebble mills are used to avoid contamination by metal of the material being ground, to avoid rapid wear due to corrosion, and for other specialized reasons. Belgian silex (silica) blocks formerly were used widely for lining pebble mills, because of their good resistance to wear, light color, and low cost, but the importation of these blocks was suspended early in the war. The stocks of Belgian silex diminished so rapidly that it was found desirable to compare the properties of a number of domestic substitutes for use in critical operations. Accordingly, a study was made to determine the best substitutes for fine grinding of white pigment and for certain heavy-chemical process work such as the disintegration of phosphate rock in weak phosphoric acid solution. A comprehensive survey of substitute lining materials was not contemplated. It was stipulated at the beginning of the investigation that only materials on the market, available in large quantities, would be tested and that these should be reasonable substitutes from a a ance viewpoint as determined from known physical characteristics. Marble and limestone, for example, could be eliminated immediately. Quartzite, granite and porcelain were selected as likely substitutes for Belgian silex and were subjected to quality tests. Materials Tested 1. Belgian Si1ex.—Sample blocks of a standard grade were taken from crates in which they had been imported. The stone was light gray in color and contained inclusions of small clusters of quartz crystals as well as light colored portions that might be calcite. This was a siliceous rock which appeared to be of igneous origin. 2. Quartzite.—Samples of quartzite were obtained from a quarry in Minnesota. The blocks exhibited a crystalline fracture. The stone was pink in color and composed of fine quartz crystals bound together with a siliceous cement. 3. Granite A was a fine-grained granite quarried in South Carolina. 4. Granite B was coarse-grained granite quarried in South Carolina. 5. Granite C was a coarse-grained granite quarried in North Carolina. 6. Porcelain A.—Sample blocks of the pebble-mill lining material were obtained direct from the manufacturer. It was white in color and of lower specific gravity than the natural materials. It did not have a crystalline structure. 7. Porcelain B.—Sample pebble-mill lining blocks of the porcelain were received direct from the manufacturer. It was white

Jan 1, 1948

By R. J. Marcotte, C. T. Eddy, R. J. Smith

The objectives of the investigation herein reported were to determine: (I) the S-curves for certain selected cast steels, (2) whether or not the published S-curves for wrought steels are satisfactory for use on cast steels of similar composition, and (3) to prepare hardenability curves of the selected cast steels. In order to make the final comparisons between cast and wrought steel more completely tangible, it was deemed advisable not only to determine S-curves for the steels submitted in the cast condition but also to roll some of the cast-steel test bars and determine comparison S-curves on such wrought material. This procedure eliminates the composition variable and makes it possible to reveal the differences resulting from plastic deformation of the cast structure in addition to providing the comparison with published data on wrought steels. Cast Steels The cast steels selected for the preparation of S-curves, or time-temperature transformation curves, were similar to S.A.E. series 1030, 2330, 4130 and 4330. Of these the 1030 was supplied by The Crucible Steel Casting Co., Cleveland, Ohio, and the other three by The Sawbrook Steel Castings Co., Lockland, Ohio. The steels were furnished in the as-cast condition. The manufacturers supplied the chemical analyses and the properties that could be obtained in the heat-treated condition—all of which is summarized in Table I. The metallographic and dilatometric procedures and equipment were in general standard. The specific technique employed was described in a report of the Steel

Jan 1, 1945

By Donald L. Katz

Charts for predicting the pressure to which natural gases may be expanded without hydrate formation have been prepared for gases of even gravity. Pressure-temperature curves for hydrate formation were established for gases having gravities from 0.6 to 1.0. These curves and the thermal behavior of the gases during free and adiabatic expansion were used to prepare the charts for estimating the permissible expansion of natural gases without hydrate formation. The problem was solved by L. F, Albright, W. T. Boyd, J. J. McKetta, G. Martin, P. Poettman. and A. P. Snyder.-, who are first-year graduate students in the department of Chemical and Metallurgical Engineering at the University of Michigan. This paper is essentially a summary of their results. Prediction of Conditions for Hydrate Formation in Natural Gases Each natural gas under a given pressure will form solid hydrates at a corresponding temperature provided sufficient water is present.1-5 The temperature of natural gases below about 5000 lb. per sq. in. decreases when the gases are expanded freely.6,7 This decrease in temperature may cause the expanding gas to enter the region of temperature and pressure at which hydrates will form&apos; The final pressure to which a natural gas may &apos;be expanded without hydrate formation depends upon the initial temperature and pressure and the gas composition. This paper presents charts that give the final pressures to which gases of gravity 0.6 to 1.0 at given initial temperatures and pressures may be expanded without formation of hydrate. Hydrate-forming Temperatures and Pressures as a Function OF Gas -Gravity Experimental data of pressure versus temperature at which solid hydrate will form, provided sufficient water is present, are available for a series of gases.2,3 A method of predicting the pressure-temperature curve for a given gas composition has been reported.&apos; The solution to this problem requires that these curves relating pressure to temperature be established for gases of given gravities.

Jan 1, 1945

By G. W. Binkley, G. K. Dumbauld, F. A. Brooks, B. E. Morgan

In recent years, oil well cementing compositions have been developed with low densities, controlled set strengths, and satisfactory thickening times. With the introduction of the permanent-type well completion method for cementing wells, another property—that of rate of filtration or water loss to permeable formations— has become important. Laboratory data show that cement slurries prepared with oil, water, bentonite, and calcium lignosulfonate possess satisfactory thickening times, strengths, and filtration properties for primary cementing of casing and for squeeze cementing with the permanent-type well completion technique. Cementing compositions have been prepared with oil-in-water emulsions varying in composition from 60 cc water and 20 cc oil per 100 gm cement to 90 cc water and 45 cc oil per 100 gm cement. These compositions have contained from 0.4 to 5.0 per cent calcium lignosulfonate by weight of dry cement. Slurries prepared from these compositions weigh 11.4 to 13.1 lb/ga1 and have filtration rates of from 10 cc to approximately 100 cc in 30-min API tests at room temperature. The unfiltered emulsion cements develop one-day tensile strengths of 60 to 220 psi; and the filtered mass sets to tensile strengths of 60 to 150 psi in 12 hours and develops strengths of 320 to 515 psi in seven days when cured at 125° F. Field experience gained from 13 field mixing jobs demonstrates the utility of the emulsion cement for permanent-type squeeze cementing operations. INTRODUCTION In recent years, research in oil well cementing composition has been directed toward the development of cements having low densities, controlled set strengths, satisfactory thickening times, and low rates of water loss by filtration. Two well cementing compositions that have been developed with these properties are the modified cements containing, respectively, 12 and 25 per cent bentonite clay and various concentrations of calcium lignosulfonate1,2 In a search for other ways to incorporate these characteristics in a cementing composition, consideration was given to the rheological properties of oil-emulsion drilling fluids. Many of the desirable properties observed in oil-emulsion drilling fluids are equally advantageous in a cementing composition. For example, low water loss by filtration and low density, which are inherent characteristics of these oil-in-water emulsions, are desirable for many oil well cementing operations. Furthermore, oil-emulsion slurries have lubricating properties similar to those of oil-emulsion muds, a factor which should provide ease of rotation of casing during primary cementing operations. The properties of lubrication and low filtration may be of special value in both primary and squeeze cementing operations encountered in slim-hole drilling. Studies in the preparation of oil emulsion systems have pointed out the need for violent agitation in order to disperse the oil into the water phase. It was thought, therefore,

Jan 1, 1957

By W. R. Seyfried

THE problem of extracting alumina from clay and low-grade bauxites has been the subject of considerable interest for some time. The basic reason, of course, lies in the fact that known reserves of high-grade bauxite are not inexhaustible and that the present commercial process cannot successfully cope with low-grade bauxites or clay. Ultimately it may be necessary to use these poorer raw materials for all commercial operations. An unprecedented demand for aluminum during the war emergency and the constantly threatened shortage of imported bauxite caused the United States Government to take an active role in this problem. Through the National Academy of Sciences, the War Production Board and the Defense Plant Corporation, it investigated processes and finally selected four to be used in the construction and operation of four experimental plants. Each plant was to be designed in such a way as to facilitate its incorporation into a larger commercial plant should the need arise. The Chemical Construction Corporation process, or "Chemico" ammonium sulphate process as it is better known, was one of the four selected. The extensive literature and patents on record before the war generally follow one of two process-types depending upon the extracting reagent used. One group uses an acid reagent, the other an alkali. The Chemico process uses an acid reagent. For those interested in other processes described in literature, there is a short bibliography at the end of this paper. The basic steps of all acid extraction processes are: (I) to make the aluminum silicates acid soluble, (2) to separate the released alumina from impurities and insoluble gangue, and (3) to recover the reagent for re-use. THE PROCESS AS PLANNED In April 1941, a group of chemists and engineers of the Chemical Construction Corp. became interested in the problem of extracting alumina from clays and low-grade bauxites and, under the leadership of Mr. Blakeslee Barnes, Vice President and General Manager of the Company, first drafted a process in July of that year-five months prior to Pearl Harbor. The work continued in our research laboratories and with a small pilot plant. By June 1943, the work had progressed to a point where it was possible to apply for a patent on the process which was U.S. patent 2,405,426, granted August 6, 1946. Immediately prior to the development of the Salem plant, the process was envisaged to be as follows: I. The first step was to make the aluminum silicates acid soluble. It was planned: (a) Clay or low-grade bauxite would be roasted at 700 to 800°C (1292° to 1472°F), (b) The roasted ore would then be leached with hot aqueous ammonium bisulphate to form a slurry. In this way the

Jan 1, 1947

By R. H. Jacoby, V. J. Berry

Future depletion performance and ultimate oil recovery from reservoirs producing under volumetric control are often predicted with the aid of a material balance equation. When the reservoir fluid is very volatile, however, certain assumptions implicit in the use of the conventional methods are no longer valid. This is became laboratory differential vaporization test procedures do not adequately represent the reservoir depletion process and the performance of surface separation facilities. In such cases recovery of stock tank oil per unit of pressure decline can be predicted only from a detailed knowledge of the separator conditions and the over-all composition of the fluid entering the wellbore at each stage of depletion. Surface recovery is not simply related to the total quantity of liquid flowing into the well under reservoir conditions. In order to improve predictions for reservoirs which produce volatile oils, a step wise method of calculation has been developed. This method uses relative permeability data and multicomponent flash calculations to predict oil and gas production as a function of reservoir pressure. Calculations are presented for a reservoir containing a volatile crude oil, and predicted tank oil recovery by primary depletion is more than twice that predicted by conventional methods which are known to be adequate for ordinary black crude oils. Calculated maximum produced gas-oil ratio is less than one-fourth of the conventional prediction. Wellstream compositions have also been used to determine variation in stock tank oil composition and liquid content of the separator gas. This information is of particular importance for crude stabilization calculations and for design of gasoline plant facilities to recover LPG and natural gasoline. INTRODUCTION The estimation of oil reserves and the prediction of future recovery performance of petroleum reservoirs is a frequent task of the petroleum engineer. If the reservoir produces under volumetric control, performance calculations for primary depletion are made by combining oil and gas material balances with the gas-oil flow characteristics of the reservoir rock. For black oil reservoirs, the Schilthuis1 type material balance is commonly employed. For gas or gas-condensate reservoirs, where only one phase is flowing under bottom-hole conditions, a more simplified material balance is used. In the period in which these material balance methods were conceived and put into practice, it was common to classify reservoirs according to the type of fluid produced as (1) black oil reservoirs, or (2) gas or gas-condensate reservoirs. Recently, however, deeper drilling and more extensive studies of reservoir fluid properties have led to the recognition of reservoir fluids with phase characteristics between those of ordinary black oils, and gases or gas-condensate fluids. These intermediate fluids contain relatively large amounts of the hydrocarbons ethane through decane and are found in deep, high temperature (250°F) reservoirs. Such fluids are often referred to as high shrinkage crudes or "volatile oils." They are usually characterized by tank oil gravities above 45° API. high solution gas/oil ratios,

Jan 1, 1958

By H. T. Clark, S. Feigenbaum

The importance of measuring the temperature of molten steel in the open-hearth furnace has been recognized for many years. Poor temperature control may be costly to steelmaking operations and lead to a lowered quality of the steel. Low or excessive temperatures may shorten the life of the furnace, ladles and molds. Rates of reactions in the furnace and efficiencies of deoxidizers are known to change materially with a change in the temperature of the metal and slag. Ladle skulls and mold and stool stickers cause steel to be scrapped instead of being converted into useful products. Finally, the structure, segregation and surface condition of ingots are affected by the teeming temperature. Mill investigations of the effect of bath temperature upon steelmaking operations have been largely qualitative in character, based upon observations by practical melting men. The physical chemist has used the empirical information available and has reached reasonable and useful conclusions with respect to the various melting processes. The introduction of a reliable direct-reading pyrometer will permit accurate quantitative evaluation of the effects of temperature and should furnish a more rational basis for study of the thermochemistry of steelmaking. The problem is not merely one of making a small numbcr of temperature measurements in the open-hearth furnace. This has been done by several methods to a * Assistant Manager, Research and Development, Jones and Laughlin Steel Corporation, Pittsburgh, Pennsylvania. Issued as T.P. 2031 in MEtals Technology, June 1946; also in Open Hearth Proc., 1946. † Open-hearth Metallurgist, Jones and 1aughlin Steel Corporation, Aliquippa. Pennsylvania. degree of precision that was apparently satisfactory. Considerable effort by a number of investigators has been directed rather to the development of an open-hearth bath pyrometer that would be both accurate and practical for routine measurements. To be practical, the pyrometer should be inexpensive to operate; that is, the installation, operating and maintenance costs should be exceeded by the tangible benefits to the open-hearth operator. Temperatures from 2800&apos; to 3100°F. are. encountered in the open-hearth furnace. The surface of the molten metal is covered by several inches of slag, which prevents direct observation of the metal surface for optical or radiation measurements. Both slag and metal are highly reactive at these temperatures and will attack to a greater or lesser extent any material immersed in them. Adequate protectioil of thermocouples, which of necessity must be brought to the temperature of the bath, has generally resulted in a large, heavy assembly made up of brittle materials, unsuited for handling on the open-hearth floor. The life of the equipment was short and maintenance was an important consideration. Earlier Work Any of a number of Physical Properties of liquid steel could conceivably be used a a basis for temperature measurement. Efforts to the present time, however, have been confined largely to measuring either the thermal electromotive force generated between two dissimilar materials immersed in the steel or the intensity of radiation from the surface of the steel. These

Jan 1, 1947

By H. T. Clark, S. Feigenbaum

The importance of measuring the temperature of molten steel in the open-hearth furnace has been recognized for many years. Poor temperature control may be costly to steelmaking operations and lead to a lowered quality of the steel. Low or excessive temperatures may shorten the life of the furnace, ladles and molds. Rates of reactions in the furnace and efficiencies of deoxidizers are known to change materially with a change in the temperature of the metal and slag. Ladle skulls and mold and stool stickers cause steel to be scrapped instead of being converted into useful products. Finally, the structure, segregation and surface condition of ingots are affected by the teeming temperature. Mill investigations of the effect of bath temperature upon steelmaking operations have been largely qualitative in character, based upon observations by practical melting men. The physical chemist has used the empirical information available and has reached reasonable and useful conclusions with respect to the various melting processes. The introduction of a reliable direct-reading pyrometer will permit accurate quantitative evaluation of the effects of temperature and should furnish a more rational basis for study of the thermochemistry of steelmaking. The problem is not merely one of making a small numbcr of temperature measurements in the open-hearth furnace. This has been done by several methods to a * Assistant Manager, Research and Development, Jones and Laughlin Steel Corporation, Pittsburgh, Pennsylvania. Issued as T.P. 2031 in MEtals Technology, June 1946; also in Open Hearth Proc., 1946. † Open-hearth Metallurgist, Jones and 1aughlin Steel Corporation, Aliquippa. Pennsylvania. degree of precision that was apparently satisfactory. Considerable effort by a number of investigators has been directed rather to the development of an open-hearth bath pyrometer that would be both accurate and practical for routine measurements. To be practical, the pyrometer should be inexpensive to operate; that is, the installation, operating and maintenance costs should be exceeded by the tangible benefits to the open-hearth operator. Temperatures from 2800&apos; to 3100°F. are. encountered in the open-hearth furnace. The surface of the molten metal is covered by several inches of slag, which prevents direct observation of the metal surface for optical or radiation measurements. Both slag and metal are highly reactive at these temperatures and will attack to a greater or lesser extent any material immersed in them. Adequate protectioil of thermocouples, which of necessity must be brought to the temperature of the bath, has generally resulted in a large, heavy assembly made up of brittle materials, unsuited for handling on the open-hearth floor. The life of the equipment was short and maintenance was an important consideration. Earlier Work Any of a number of Physical Properties of liquid steel could conceivably be used a a basis for temperature measurement. Efforts to the present time, however, have been confined largely to measuring either the thermal electromotive force generated between two dissimilar materials immersed in the steel or the intensity of radiation from the surface of the steel. These

Jan 1, 1947

HeRbeRT Haas,—(communication to the Secretary*).—Fig. I plainly shows that the comparison of the steam-turbine and Diesel-engine plants was made on a basis of 6,000 kw. continuous operating load. The tabulation of costs for an 8,000-kw. load is merely done to show the relation of increased output on the unit power costs. Both plants would sacrifice their reserve capacity, which is to insure continuous operation, if operated to generate 8,000 kw. continuously; unless Mr. Hawkins advocates the operation of one of the turbines at 33.33 per cent. overload, retaining the other as a standby, which, besides overtaxing the turbine, results in a great loss of efficiency. It would be well for Mr. Hawkins to qualify certain of his statements. Thus, under the caption "Diesel Engines, Selection of Units," he says that &apos;(two of the largest Diesel-engine builders take the position that, in the present state of the art, they would not attempt to put out units over 1,000 kw.;" he should qualify it by saying that "two of the largest American Diesel-engine builders take the position that, in the present state of the art in the United States, they would not attempt to put out units over 1,000 kw." The reason that American manufacturers restrict themselves at present to units of that size is to be found not so much in a lack of experience in building large units as in a lack of a sufficient demand for them in the United States to justify the heavy capital outlay connected with the development of such engines. There are relatively few localities in the United States where fuel prices are as high as they are in the South-, west, and regions of high fuel prices are sparsely settled and have a very limited demand for power. Where low fuel prices obtain, steam turbines are active competitors of Diesel engines for large power plants, particularly when the station load factor is low. As most of the American manufacturers of Diesel engines work under license agreements with European manufacturers, which limit their market to the United States and its possessions and Canada, a further limitation is imposed upon them, leaving to European firms practically the entire world as a market. The greater number of power plants range in size from 300 to 1,000 hp.; the average size of the central station, on a basis of all central stations in the United States, not greatly exceeding 500 kw.; in these sizes it is hard for steam engines to compete with Diesel engines, unless fuol oil prices are excessively high, and coal prices very low, or the exhaust steam is used for heating purposes.

Jan 1, 1917

By Burnham E. Field

TAE chemical industry is constantly looking for new materials which either are more resistant to corrosion than those now available or have improved physical properties to meet the requirements of higher temperatures and greater pressures. Attack by acids is-one of the more important forms of corrosion-and in the last few years the development of acid-resistant alloys has been quite rapid. Perhaps the most notable example is that of nitric acid, &apos;the problem of which has largely been solved by the chromium-iron and chromium-iron-nickel alloys. Sulfuric acid may be handled in lead, iron, or the iron-silicon alloys, depending on conditions. As to hydrochloric acid, no metal or alloy can be called entirely satisfactory for handling. this acid under plant conditions.1 The results of our investigations on the resistance of the nickel-molybdenum alloys to hydrochloric acid have been confirmed by those of Guertler, Rohn, Schulz, Jenge, and others,&apos; but thus far only one such alloy has approached commercial production in Germany; this contains approximately 15 per cent. chromium and 7 per cent. molybdenum with the remainder chiefly nickel. Dr. S. W. Parr, as far back as 1914, developed a complex alloy known as "illium," with a nickel base and containing some molybdenum.3 Dr. Parr was primarily interested in an alloy for lining bomb calorimeters, and while illium does show good resistance to acid it is too expensive for general use. Two United States

Jan 1, 1929

By L. E. Murr, P. J. Smith

A study has been made by transmission electron microscopy of thin foils of 304 stainless steel fatigued external to the electron microscope in reversed bending, and of thin foils fatigued directly within the microscope in alternating tension. The build-up of stacking faults in the thin foils during fatigue zoas correlated with the dislocatirm structures found in thin films prepared fror fatigued bulk specimens. The performance of the special devices designed for fatigue of thin foils so outlined and the importance of alternative methods of preparation of more uniform fatigue specimens bY vapor deposition are emphasized. INVESTIGATIONS on fatigued bulk aluminum1,&apos; and stainless stee13j4 have revealed the existence of dislocation substructure on examination by transmission electron microscopy of electrolytically thinned foils representative of these bulk specimens. While this technique has proved extremely valuable, it has several shortcomings. First, the method of fatiguing bulk specimens and then thinning to foil for electron-transmission observation allows only one observation of internal structure at any one portion of the fatigue life. Second, thinning the bulk fatigued specimens to foil results in the loss of at least one original surface. Thus, what one sees in the remaining electron-transparent sections is an internal dislocation or fault structure which in many cases cannot be correlated with the original surface markings. This is an undesirable feature, since it is well-known that metal surfaces play an important part in the fatigue process.5 An obvious third undesirable feature of the thinning-from-bulk technique is the fact that static observations have difficulty (in the case of fatigue) explaining the mechanism of a dynamic process. What is required then is a method whereby a selected thin area can be continuously observed either while undergoing cyclic deformation or at various fixed stages of fatigue deformation. While Murr and wilkov6 have reported some success with an apparatus designed to fatigue thin metal foils directly within the electron microscope, the nature of the specimen-mounting procedure and the mechanical features involved in the adaptation of the fatigue device to the electron microscope make this method difficult to operate. It was not possible, for example, to make frequent observations of a selected area because of difficulty in maintaining a chosen area in a stable viewing position inside the electron microscope. Except for the build-up of a dislocation substructure and what are commonly referred to as "slip striations", little else has been reported from observations on thin-foil sections prepared from bulk fatigue specimens. segal17 has found "slip striations" in stainless-steel fatigued specimens which were electropolished from both sides, but gave no explanation as to their origin or identity in terms of lattice imperfections. The research to be reported in this paper was undertaken with the following objectives in mind. First, an attempt was made to devise a technique or techniques whereby thin metal foils could be fatigued and repeatedly observed by transmission electron microscopy. Second, it was hoped that some correlation could be made between deformation striations found in fatigued thin transmission specimens and thin foils prepared from bulk fatigued specimens. These investigations illustrate quite convincingly that a feasible method is available for the direct study of the fatigue mechanism and similar dynamic phenomena in thin transmission specimens inside the electron microscope. I) EXPERIMENTAL METHODS Three modes of specimen fatigue and observation of fatigue damage were used. These involved fatigue of thin-foil specimens in a special arrangement external to the electron microscope and observation of a selected area at various stages in the fatigue life, the fatigue of thin-foil transmission specimens inside the electron microscope, and the fatigue of bulk specimens external to the electron microscope followed by thin-foil preparation for direct observation at predetermined stages. Design of the External Fatigue Clip and Specimen Holder for the Hitachi H.U.11 Electron Micro-scope. The purpose of the fatigue clip was to provide a reversed bending fatigue stress to a thin-foil transmission specimen outside the electron microscope. In order to accomplish this, a flat-bottomed, U-shaped brass clip was made as shown

Jan 1, 1965

By William D. Klopp, Joseph R. Stephens

Chromium alloys were coated with silicon, alumi-nuw, and boron by pack cementation. None of these simple coatings provided adequate nitridation/oxida-tion protection for a Cr -0.17pct Y alloy substrate as shown by a substantial Increase in the ductile -brittle transition temperature after air exposure for 100 hr at 2100°F. Iron-modified silicide coatings afforded good protection, holding the transition temperature of air-exposed specimens to 350° F compared to 200° F for uncoated unexposed specimens and 800°F for un-coated exposed specimens. Additional attractive cant-binations of modi-tying elements included Fe-mo, Fe-Mo-W, Fe-,Mo-W-Ti, and V-Mo-W-Ti. THE desirability of increased operating tempera-tures as a mcans of improving the performance of ad-vanced air breathing engines has resulted in emphasis on the development of materials with high operating temperature capabilities. Chromium, because of its relatively low density (7.19 g per cu cm), high melt-ing point (3410°F), and adequate strength upon alloy-ing, is a candidate material for turbine buckets and stator vanes of advanced air breathing engines. How-even, chromium is not without severe limitations, the major one being susceptibility to nitrogen embrittle-ment upon exposure to air at high temperatures.1,2 For example, a 25-hr air exposure of a Cr-5 pct W* * All compositions in wt pct. alloy at 2100°F produces a 600°F increase in the duc-tile-brittle transition temperature.&apos; Although dilute alloying with such elements as yttrium, lanthanum, arid thorium3,4 or strong nitride formers5 has been shown capable of reducing nitrogen embrittlement, it is apparent that some additional form of surface protection, such as coatings or claddings, will be required for long time service in air breathing engines. Studies of aluiminide6 and silicide7 coatings and of nickel-base claddingsl on chromium alloys to date have suggested that these protection systems are inadequate. Of the aluminidc systems Studied,6 a simple aluminum and an Fe-Al coating on a Cr-5 pct W-0.1 pct Y alloy showed the lowest air exposure weight gains. However, the air exposures raised the ductile-brittle transition temperature of the coated specimens to above 1600°F from an initial level in unexposed specimens of about 500°F. A second in-vestigation for protection of Cr-5 pct W-0.1 pct Y employed gas pressure bonded alloy foils as protective claddings.1 An aluminized Ni-20 pct Cr-20 pct W alloy plus an unalloyed tungsten barrier layer gave the best performance with air exposure lives based on appearance and weight gains of over 600 hr at 2100°F. However, the bend ductile-brittle transition tempera-ture was increased to at least 1000°F after 100 hr at

Jan 1, 1970

By G. Y. Chin, M. T. Dolan, W. L. Mammel

The least work analysis of constrained deformation, first proposed by Taylor and recently modified by Chin, Hosford, and Mendorf to include twinning, has been applied to the problem of axisynmetric flow. Calculations were made, for the case of (111}(110) slip and {111}(112) twinning applicable to fcc deformation. The solutions were obtained by linear programming techniques and with the aid of computer methods. The results show that in axisymnzetric tension the onset of twinning tends to decrease the plastic strength anisotropy as compared with the case of defortnation by slip alone. In compression, however, the strength anisotropy is increased as a result of twinning. The [100] and 11111 orientations and their vicinity are unfavorable for twinning in tension and compression, respecticely. With slight modifications, the present results may be applied to bcc metals deform ing by {110}(111j slip and (112} (111) twinning. Implications of present results to wire texture development of low stacking fault energy fcc materials arc discussed. PREVIOUSLY we&apos; have applied linear programming techniques to obtain solutions to Taylor&apos;s least work analysis2 of constrained deformation of single crystals undergoing axisymmetric flow, such as occurs in an axially loaded polycrystalline aggregate. These solutions yielded values of the parameter M = o/.r = Y/w which relates the external stress-strain (u-c) curve to the shear stress-shear strain (7-y) curve for the crystal. The value of M is dependent on crystal orientation and hence enters significantly in texture strengthening considerations.3&apos;4 Recently the Taylor hypothesis was modified by Chin, Hosford, and Mendorf&apos; to include mechanical twinning. The latter has now been applied to the problem of axisymmetric flow and the results are reported in this paper. Calculations have been made for {111 )( 110) slip and {111 )(112) twinning applicable to fcc crystals. With minor changes in the indices of the slip and twin systems, the present results are also applicable to bcc crystals which slip on (110) (111) and twin on {112)(111) systems.

Jan 1, 1970

By Craig S. Hartley

An approximate expression is obtained for the energy of a closed dislocation loop in equi1ibriu)n with a constant net stress. The result obtained is valid for loops in isotropic or anisotropzc materials provided that they are suJficiently large that the energy per unit length of a segment of the loop can be approximated by that of an infinite straight dislocation tangent to the loop. It is shown that this approximation leads to very close agreement with a more rigorous calculation of the elastic energy of a circular glide loop. The Gibbs-Wulff Form, GWF, of a dislocation is the closed planar loop which has the smallest elastic self-energy of all possible loops having the same Burgers vector and enclosing a fixed area, A.&apos; The energy of such a loop is related to the net resolved shear stress* required to expand the loop and to the stress required to activate a Frank-Read source.223 In the following sectiorls the problem of determining the form of the GWF is discussed and an approximate method for calculating its elastic self-energy is presented. It is demonstrated that the approximations employed lead to no serious errors when applied to a calculation of the elastic energy of a circular glide loop. This method is then used to obtain a closed form expression for the energy of GWFs in isotropic and anisotropic materials. THEORY Burton, Frank, and cabrera4 have proved that the relationship of the equilibrium shape of a two-dimensional array of atoms under the influence of the Gibbs free energy associated with unit length of its boundary, G(O), is that the polar plot of G(0) vs 0 is proportional to the pedal of the GWF.* The angle 0 is measured "The pedal of the polar graph ofG(0) vs0 is the envelope of tangents to the eraph.relative to some crystallographic reference direction. The difficulty in applying this result to a closed dislocation loop arises from the self-interaction of the loop. For a dislocation the energy analogous to G(0) is a function of the total configurati~n.~ Consequently the relation which determines the GWF is an integro-differential equation rather than the simple differen- tial equation which results when G(8) is a function of 0 alone. Mitchell and smialek3 and Brown~ have used the self-stress concept introduced by ~rown&apos; to calculate the shapes of dislocations in equilibrium with an applied stress. In this approach the glide force on an element of the dislocation loop due to the interaction of the element with the rest of the loop is equated to the glide force exerted by the local applied stress. The shape of the loop is then adjusted so that the two forces above are equal at all points on the loop. It is possible to calculate the energies of such loops by noting that, for equilibrium with an applied stress, the energy is equal to pijbiAj (summation convention) where bi is the Burgers vector, p.. is the local net stress tensor, and Ai is a vector directed perpendicular to the plane of thd loop with magnitude equal to the area of the loop. Also Brown&apos; has calculated the energy of a hypothetical polygonal GWF using the above technique and anisotropic elasticity. However, his indicated solution for the energy in the general case of an arbitrary GWF is only slightly less involved than an iterative solution of the integrodifferential equation referred to earlier. In the present work the approximation employed by DeWit and Koehler&apos; is used to calculate the energy of a closed loop in equilibrium with an applied stress. That is, the energy of a loop segment, ds, is approximated by the product of ds and the energy per unit length of an infinite, straight dislocation in a cylinder coaxial with the tangent to the loop at the angular position of the segment. This is known as the "line tension" approximation. The inner cutoff radius of the elastic solution defines the core radius, while the outer cutoff radius is determined by some characteristic dimension of the loop. Actually, both of these radii vary with the edge-screw character of the segment. The effective core radius changes because of the orientation dependence of the Peierls width of a dislocation,8 and the outer radius should be the radial distance from the circumference of the loop to the center of symmetry of the area enclosed by the loop.g However, since the energy varies logarithmically with the ratio of these radii while depending directly on the effective elastic constants, only the effect of the latter is considered. This approximation also neglects the self-interaction of the loop segments. For small loops this will doubtless be extremely important, but for large glide loops produced by plastic deformation the self-interaction is not nearly so important in determining the energy of the loop. This point is illustrated by the following calculation of the energy of a circular loop. Consider a circular loop of radius R which lies in the XI - x, plane of an infinite isotropic continuum and whose Burgers vector makes an angle $ with xs. The first-order solution for the elastic self-energy is:&apos;

Jan 1, 1970