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By K. E. Beu

IN the measurement of retained austenite concentrations in steels using the integrated intensity method,1 Averbach has pointed out" that the absorption factor A(0) for a flat sample making a glancing angle 4 with the incident X-ray beam can be combined with his constant factor R to obtain our constant factor" G provided that "1—There is no preferred orientation in the sample, and 2—The geometric requirements [for the sample, film, and X-ray beam] have been met precisely."' If A(0) can be combined with R to give G according to the equation G = R . A(0) [14] then the possibility for making non-compensating errors in the austenite determination has been eliminated. This has been described previously in a technical note." Because of the brevity of the previous note,3 it was impossible to emphasize the fact that the two conditions on preferred orientation and geometry can be easily met experimentally, contrary to Aver-bach's statement that: ". . . the necessary conditions must be tested experimentally for each determination, and this is done most easily by observing whether the apparent absorption has the form of Eq. 2 [the theoretical equation for A(0)]."" he way in which these two conditions can be met experimentally will be discussed briefly to help clear up this point. In addition to these two conditions, other factors such as sample shape, homogeneity, and grain size which also affect A will be included in this discussion. A (0) depends on sample shape. The theoretical function for A was derived originally for a flat surface.' In general we have found that a flat sample surface is readily obtainable." If such a surface can * The effect of surfaces which are not flat on the measurement of retained austenite will be discussed later. be obtained, it has the following advantages: 1—it is easily reproducible from sample to sample, 2—it is the form required for metallurgical examination —this type of examination being frequently desirable for this work, and 3—it is an efficient shape for diffraction purposes. Perhaps the most important of these features is that a flat sample surface is easily reproducible; hence, this requirement on the repro-ducibility of A from sample to sample is met for all such samples. Fig. 1—Schematic diagram of the quartz crystal monochromator diffraction unit. The centerline of the main beam is at 6' to the target face. The tangent to the crystal face is at 16.8' to the moin beam. The centerline of the monochromatic beam is at 33.6 to the main beam. The sample surface can be rotated in its own plane. The angle of the sample surface and the monochromatic beam can be adjusted by rotating about the vertical axis, The film holder can also be rotated about B so that the film can be exposed over the desired angular range. For Fe K, X = 1.932A. 1011 planes of quartz have d = 3.35A. A(0) depends on homogeneity and grain size. If the sample is badly segregated or the grain size is large, the effect of micro-absorption and primary extinction1. ' must be considered. It has been shown, however, that for most plain carbon or low alloy hardened steels, neither micro-absorption nor primary extinction effects are present.' A (0) depends on camera geometry. For a given angle 0, A remains theoretically constant from a geometrical viewpoint only if the following factors are kept constant: 1—the angle of inclination .+ of the sample to the X-ray beam, and 2—the centering of the sample with respect to the film cylinder. These are mechanical problems which can be solved readily if the facilities of a good machine shop are available. The arrangement used to insure that the angle 4 remains constant and the centering of the sample is reproducible is indicated schematically in Fig. 1. The sample is clamped against a thin plate with a hole in it by means of a spring-loaded pres-

Jan 1, 1954

By S. Shapiro, G. Krauss

RECENT investigations1 3 of the products of marten-sitic transformation in Fe-Ni and Fe-Ni-C alloys have made use of light microscopy to describe mar-tensitic fine structure. The application of conventional metallographic techniques to this problem was possible because of the similarity of distributions of parallel striations developed by etching polished surfaces to distributions of transformation twins which are positively identified in thin films by transmission electron microscopy. The surface striations frequently are not well-defined, and could also be due to, for example, rows of etch pits which are not resolved by the light microscope. This note describes the etching effects revealed by examination of surface replicas of mar-tensite in the electron microscope. The application of a replica technique both extends the observations of fine structure made with the light microscope and allows the results of conventional metallography to be used with more confidence. Samples of an Fe-33 wt pct Ni alloy were used for this study because of the detailed knowledge of the fine structure of martensite which has been developed'-4 for alloys of about this composition. Samples transformed to martensite at -120°C, and transformed samples heated to 340°C to effect a small amount of reversal of martensite to austenite, were examined. Surfaces were first prepared for replication by elec-tropolishing in a chromium oxide-acetic acid electrolyte at a current density of 0.1 amp per sq cm and a temperature of 15°C or a perchloric acid-acetic acid electrolyte at a current density of approximately 2 amps per sq cm and a temperature of 15°C. The polished surfaces were then etched for 4 to 7 sec by immersion in a solution of equal parts HC1, HNO,, and H20. Application of the etchant for this period of time produced discrete attack of certain features without loss of resolution due to overlapping of areas most susceptible to etching. The etched surfaces were replicated by 1) preshadowing with Pt-Pd alloy at an angle of 20 to 30 deg, 2) depositing a thin carbon film, and 3) stripping the film and shadowing material by immersion in a 5 pct nital solution. Two types of etching effects were observed by examination of the surface replicas in the electron microscope: l) continuous striations centered at the bottom of long grooves or the tops of pyramidal elevations on the sample surface, and 2) high densities of fine etch pits. Examples of both types of features are shown in Figs. 1 to 4. The striations are in each case continuous and have the same characteristic configurations as do transformation twins in martensite. Fig. 1 shows that the density of grooves decreases toward the edge of a martensite plate and Fig. 2 shows a region where the striations are of varying length. Similar examples of transformation twin arrangements determined by transmission electron microscopy of thinned foils of martensite have been shown in the literature,'~ and, based on these similarities, the striations and their associated grooves or mounds are considered to be evidence for the presence of transformation twins. The transf~rmation twins in martensite are on the order of l00 A thick, much too fine for resolution by the light microscope. It appears that orientation-dependent etching of the matrix martensite about the twins results in grooves or surface elevations which

Jan 1, 1967

Jan 1, 1889

By M. Semchyshen, A. P. Coldren, W. G. Scholz

A survey of the Fe-Mo-B system was made to determine the extent to which boron might affect the microstructure and strength properties of iron-rich Fe-Mo alloys. Seventeen vacuum-induc tion melted ingots were prepared with approximate mo-lybednum contents 01 2, 4, 9, and 19 wt pct and approximate boron contents of 5, 14,50, and 630 ppm by weight. Phases extracted from annealed specimens and identified by X-ray diffraction analysis included E Fe3MO2, Mo2FeB2, and an oxide hazling a diffraction pattern practically identical to that of MnFez04. Three types of alloy strengthening were observed: a) Fe-2 pct Mo-B alloys were hardenable by a bainitic-type transformtion of austenite to ferrile; b) Fe-4 pct Mo-B alloys were hardened by the solid-solution mechanism; and C) Fe-9 pct Mo-B and Fe-19 pct Mo-B alloys were hardened by precipitation of the E Fe3Moz phase. Boron was observed to have a very strong hardening effect in the Fe-2 pct Mo alloys and a mild strengthening effect on the 1200°F properties of the Fe-4 pct Mo alloys. In the Fe-9 pct Mo alloys there was no consistent effect of boron on strength at either room temperature or 1200° F. The Fe-19 pct Mo alloys were so brittle that meaningful tensile or creep-rupture data could not he obtained. No dispersion hardening from borides was recognized in any of the alloys. THE high-temperature properties of iron-rich Fe-Mo alloys were studied by Reiter and Hibbard.' They found that the strength of the alloys increased markedly as the molybdenum content was raised from 0 to 15.9 pct by weight. The authors explained the various degrees of strengthening in terms of a) solid-solution strengthening, b) strengthening from a martensitic-type transformation, and C) precipitation strengthening. The objective of the present investigation was to conduct a survey of the iron-rich portion of the Fe-Mo-B system to determine whether the beneficial effects of molybdenum on the strength of iron can be enhanced by the presence of boron. It was thought that perhaps fine dispersions of molybdenum- rich borides would be found which could improve the high-temperature strength of ferritic alloys beyond the strengths attainable by molybdenum additions alone. Also, it was considered worthwhile to study the effects of boron in alloys which are essentially free of carbon. Most, if not all, of our present knowledge about boron in high-temperature alloys pertains to alloys containing carbon and carbides. EXPERIMENTAL PROCEDURES Alloy Preparation. Seventeen 8-lb ingots were prepared from electrolytic Plastiron, unalloyed molybdenum chips, and boron powder by a vacuum-induction melting procedure employing hydrogen as the main deoxidizer. The alloys were melted in alumina crucibles using 35-lb melts, with each melt being split four ways to achieve varying boron contents within four Fe-Mo base compositions. The results of chemical analyses conducted on chips machined from the chilled ends of the ingots are presented in Table I. The boron analyses were performed by a spectrographic method utilizing primary standards prepared from boric acid. They indicated that in ingots to which no boron was

Jan 1, 1964

By O. N. Carlson, D. G. Alexander

THE hardness anisotropy of metals and alloys has been of increasing interest in recent years but silicon ferrite,1 niobium,2 and tungsten3,4 are the only bcc metals about which this type of information has been reported. This investigation was carried out on vanadium and chromium single crystals in an effort to determine to what degree the hardness variations observed in these metals are due to orientation effects and to compare their behavior with other bcc metals. In earlier work the authors had observed a small angular dependence in the Diamond Pyramid Hardness of single crystalline vanadium on the (100) plane but no anisotropic effects were noted on either the (110) or (111) planes. At the suggestion of R. G. wheeler5 it was decided to investigate this effect in greater detail using the more asymmetric Knoop indentor. The vanadium metal used in the study was prepared by the aluminothermic reduction of V2O5 followed by electron beam melting.6 The principal analyzed impurities were 230 ppm C, 230 ppm O, 65 ppm N, 90 pprn Al, Cr not detected, 50 ppm Fe, 60 ppm Ni, and 200 ppm Si. The chromium was an iodide-refined product obtained from the Chromalloy Corporation. Analysis of this material showed the following amounts of impurities present: 10 ppm C, 9 ppm O, 2 ppm N, 0.4 ppm H, 3 ppm Al, 2 ppm Ca, 2 ppm Cu, 20 ppm Fe, 1 ppm Mg, 0.3 ppm Mn, 1 ppm Mo, 3 ppm Ni, 10 ppm Si, and 1 ppm V. Single crystals of both metals about 1 cm in diam and 10 cm in length were grown by an arc-zone melt- ing technique.7 The chromium crystal was annealed at 1600°C for 6 hr in a purified argon atmosphere to remove any strains or inhomogeneities, but the vanadium was tested in the as-grown condition. The crystals were oriented by the Laue back-reflection method and then sectioned with a spark cutter into individual specimens with a (loo), (110), or (111) plane parallel to the crystal surface. They were mounted in Lucite and carefully ground to a flat surface. The vanadium specimens were then electropolished in a 6 pct perchloric acid-methanol mixture while the chromium specimens were mechanically polished on a Syntron vibratory polisher using an alumina abrasive. The orientation of each crystal was then rechecked by the back-reflection X-ray method. All of them were found to lie within 2 deg of the desired orientation with the exception of the (110)-Oriented chromium crystal which was within 4 deg. Microhardness impressions were taken at 10 deg intervals from the common (110) direction by rotating the crystal in the plane of the crystal surface. A Knoop indentor was used with a 400-g load on the vanadium crystals and an 800-g load on the chromium. The hardness values are averages of 6 impressions and standard deviations were calculated for each set of data. The values reported for the (111) plane of vanadium are based on from 10 to 15 measurements for each point. The microhardness results for vanadium and chromium are plotted as a function of the angular rotation of the long axis of a Knoop indentor from the (110)

Jan 1, 1970

By W. L. Fink, L. A. Willey

DURING the war there was introduced a new higher strength aircraft alloy designated 75S.1,2.3 The properties of this alloy assure extensive applications in both military and commercial aircraft. It is therefore important to understand its limitations as well as advantages. The properties of 75S alloy in the heat-treated tempers, like those of many other aluminum alloys, are affected by the rate of quenching. In general, low quenching rates tend to cause low strengths and to adversely affect the resistance to corrosion. Commercial quenching procedures are usually sufficiently rapid to permit the development of maximum properties. However, in the center of heavy sections, such as large rolled and extruded shapes, the quenching rates may not be rapid enough to develop maximum strength or resistance to corrosion. The investigations of 75S alloy described herein reveal the most critical range of temperature and the effects of quenching sheet and extrusions at different rates through that temperature range, on the tensile properties and resistance to corrosion. PROCEDURE Preparation of Specimens Sheet specimens (3 in. by 9 in.) were prepared from a commercial lot of 75S "as rolled" sheet (0.064 in. thick). The composition° was as follows: Weight Percentage Cu Mn Mg Zn Cr Al with Normal Impurities 1.64 0.16 2.58 5.66 0.27 Remainder The specimens employed for the determination of the time-temperature relations during quenching of sheet were prepared by the following procedure: the hot junction of a 28-ga. iron-constantan thermoelement (asbestos insulated) was brazed to a thin strip of aluminum which was in turn brazed into the end of a 3/16 in. i.d. by ¼ -in. o.d. by 30 in. long aluminum protection tube. Before brazing, the tube was flattened to 0.064 in. thickness over the junction and adjacent lead wires for a distance of 1 ½ in. The flattened end of the tube was fitted into a slot cut from one edge to the center of the 3 in. by 9 in. by 0.064 in. sheet and brazed into place. The brazed joint was dressed to the thickness of the sheet and the entire specimen buffed to approximately the brightness of "as rolled" material. Because of the brazing operations required, these specimens were prepared using 3S alloy. For the investigation of quenching rates in heavy sections, there were used 75S extrusions which had compositions similar to that of the sheet. The specimens consisted of 14 in. lengths of ¾ in., 2 in., 3 in. and 4 in. diam cylindrical rods and a roughly rectangular extruded section which was approximately 4 in. by 7 ½ in. Thermocouples were peened into the bottoms of 1/8 in. diam wells drilled into one end and parallel to the axis to a depth of

Jan 1, 1947

By A. G. H. Anderson, A. W. Kingsbury

Silicon bronzes containing ken are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 etermined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at iioo°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West? have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,l,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. Preparation of Samples Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 1/8 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1943

By A. G. H. Anderson, A. W. Kingsbury

Silicon bronzes containing ken are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 etermined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at iioo°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West? have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,l,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. Preparation of Samples Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 1/8 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1943

By A. G. H. Andersen, A. W. Kingsbury

SILICON bronzes containing iron are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith' and of A. G. H. Andersen .2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 determined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at 1100°C. Hanson and Ford," using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. Of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West7 have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,1,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. PREPARATION OF SAMPLES Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates h in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1942

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3'4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By Benjamin Lustman, Robert F. Mehl

The study of the high-temperature oxidation of pure metals, intensively pursued experimentally since the pioneer work of Pilling and Bedworth1 and supplemented by the recent theoretical work of Wagner2 is now well advanced. The important field of low-temperature oxidation—i.e., oxidation extending only through the temper color range of thicknesses with the formation of thin oxide layers in the range from 0 to 1000-2000 ?ngstroms—has not, however, reached so satisfactory a state, owing largely to the experimental difficulties that attend the formation and study of thin films; most of the work has been performed on abraded specimens whose surface irregularities approximated the thickness of the films formed. It has been pointed out that the rates of oxidation of different crystal faces are different and that the difierence may be related to the orientation relationships that obtain between the metal crystal and the superimposed oxide crystal; it has also been suggested that this orientation dependence should manifest itself in rates of oxidation and perhaps also of corrosion in aggregates bearing preferred orientations.3'4 An attempt to measure the rates of oxidation of different crystal faces of alpha iron demonstrated this difference in rate,4 but the dependence of rate on orientation was not simple; the method of measuring thickness, consisting of a color comparison with barium stearate multi-films of known thickness, was not wholly satisfactory. For these reasons it was felt that a study of the rate of oxidation of single crystals prepared with surfaces as smooth as possible, using a sensitive method giving true film thickness, should be profitable. Copper was chosen because of the ease of reduction of the primary oxide film and because the orientation relationships between metal and oxide and the composition of the oxide films formed at low temperatures are known; for thin films formed at low temperatures, Cu2O alone occurs.22-24 Experimental Procedure Various methods of surface preparation were attempted in order to obtain a surface that would oxidize uniformly and repro-ducibly. Electrolytic polishing by the method of Jacquet5 and electrolytic and mechanical polishing followed by annealing in vacuum and in purified hydrogen at various temperatures were tested. The procedure finally adopted consisted in a fine metallographic polish followed by an anneal in purified hydrogen at temperatures of 900° to 1000°C. for 12 hr. or more. The surface so produced was very bright and smooth, with no trace of specular etching (though some grain-boundary etching was observed); indeed, fine scratches produced by the final polish were entirely removed by the high-temperature anneal. After this treatment, the specimens were cooled in hydrogen to room temperature and placed in the oxidation furnace, where

Jan 1, 1941

By J. R. Cahoon, W. V. Youdelis

FOR the diffusion of copper in silver-rich alloys, there have been only two previous investigations, that of Seith and Peretti in 1936, and that of Sawatzky and Jaumot2 in 1957. Seith and Peretti obtained a value of 24.8 keal per g-atom for the activation energy of diffusion whereas Sawatzky and Jaumot obtained a value of 46.1 keal per g-atom. Admittedly, Seith and Peretti used relatively high concentrations of 2 at. pet Cu and polycrystalline diffusion couples, while Sawatzky and Jaumot investigated tracer diffusion in single crystals of silver. The difference in the results, however, seems too large to attribute solely to solute concentration, as a change of over 20 keal per g-atom in the activation energy suggests a change in the mechanism of diffusion. Therefore, in the present investigation the diffusion coefficient for copper in polycrystalline Ag-2 at, pet Cu alloy is re-established using conventional sandwich-type diffusion couples and electron-probe microanalyses, and the results are compared with those of the previous studies. The diffusion couples were prepared from high-purity silver (99.999 pet) and high-purity copper (99.999 pet). The silver disks, 1/4 in. long and 4 in. in diam, were machined from an ingot which had been solidified in a dynamic vacuum of 10-3 mm of Hg to eliminate oxygen absorption which otherwise would result in copper oxide precipitation in the weld zone. The alloy disks of similar dimensions were machined from an alloy ingot (nominal composition 2 at. pet Cu) which had been unidirectionally solidified to obtain a predictable solute concentration,3 and homogenized for 1 week at 800°C. Sandwich diffusion couples were made by pressure welding an alloy disk between two silver disks in an induction heating coil. The couples were diffusion-annealed at temperatures of 800°, 756°, 699°, and 630°C in tube furnaces in which the temperature was controlled to better than ± l°C. The diffusion couples were examined metallographically for weld defects, and couples showing even minute defects at the weld interfaces were rejected. Concentration penetration curves were established using an A.R.L. Microprobe analyzer. CuKO radiation was counted and converted to concentration using 0.5 and 1.0 wt pet Cu chemically analyzed standards. Initially, four continuous profiles were obtained, and averaged to obtain the final diffusion curve. The initial analysis was performed commercially and the welds were not located with respect to the profile. Therefore, the results were rechecked by the authors using the Mellon Institute A.R.L. probe. In the latter case, concentrations were obtained at 10-µ steps for four different traverses, and then averaged to obtain

Jan 1, 1968

By A. G. H. Andersen, A. W. Kingsbury

SILICON bronzes containing iron are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 determined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at 1100°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. Of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West7 have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,12, 7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. PREPARATION OF SAMPLES Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 3 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1942

By Harold Vagtborg

Equilibrium vaporization ratios were obtained for light hydrocarbons, nitrogen, carbon dioxide, and hydrogen sulfide in a reservoir fluid containing 35 mole per cent hydrogen sulfide. The data cover the range from 700 to 2500 psia at 154°F. The results of this study are compared with results obtained by other investigators on systems containing less hydrogen sulfide. When large amounts of hydrogen sulfide are present, the equilibrium vaporization ratios for ethane and heavier hydrocarbons are greater than the ratios for systems containing little or no hydrogen sulfide. Large amounts of hydrogen sulfide have the reverse effect on the ratios for methane. Routine PVT studies were performed on the reservoir fluid including flash and differential liberations of the dissolved gas. The pressure-volume relationships of the saturated fluid were also determined. It is shown that the use of published correlations on physical properties of reservoir .fluids can lead to gross errors when applied to systems containing large amounts of hydrogen sulfide. INTRODUCTION Equilibrium vaporization ratios for various components in naturally occurring crude oil and condensate systems have been reported in the literature.1,2,3,4 Recently, several papers have been published with emphasis on non-hydrocarbon components such as nitro- gen, carbon dioxide and hydrogen sulfide.5,6,7,8,9 The increased discovery of reservoir fluids having high concentrations of these non-hydrocarbon components, particularly hydrogen sulfide, has created a need for a further study of their phase behavior. Equilibrium vaporization ratios are known to vary with pressure, temperature, and overall composition of the system.'" It was anticipated that ratios for systems containing large amounts of hydrogen sulfide would differ from the ratios for systems containing small amounts of hydrogen sulfide. Therefore, the present work was undertaken in order to obtain reliable equilibrium vaporization ratios for the reservoir-fluid in question. PROCEDURE The procedure followed was evolved after considerable experimentation on methods of handling the very sour crude. It was found that drying agents (e.g. CaCl2 and CaSO4) absorbed an appreciable amount of hydrogen sulfide from the gas used to prepare the recombined samples. The concentration of hydrogen sulfide dropped as much as 10 mole per cent in a single pass through a 3-ft drying tube. It was also found that when undried gas was agitated with mercury in the PVT cell, a black scum, believed to be mercuric sulfide, was formed and the hydrogen sulfide content of the gas dropped several mole per cent. Because composition changes during a run could not be tolerated, separation of the mercury and sour fluid was necessary. In order to effect this separation, a stainless steel piston, equipped with Teflon O-rings, was placed in the PVT cell between the mercury and the sour fluid. This piston had to be constructed in three parts because

Jan 1, 1955

By L. D. Jaffe, H. C. Mann, E. L. Reed

The authors have recently published1 evidence that brittle transgranular fracture of polycrystalline metals does not originate at a point and propagate continuously across the material, but rather develops at numerous related points, leading to a series of micro-cracks which subsequently link up. Series of related microcracks were observed in steel specimens broken in fatigue—specifically, at the central portions which broke during the final sudden fracture. Microcracks of the type mentioned have also been reported by Baeyertz, Craig and Bumps'2 in steel broken under impact. % Some micrographs published by Irwin3 may possibly be interpreted as showing discontinuous brittle cracks. This paper presents additional observations of the authors on discontinuous crack propagation under various conditions. Impact Test Specimens The impact test specimens were cut longitudinally from a steel forging containing: The heat treatment consisted of oil quenching in a heavy section from 1600°F and tempering at 1260°F. The resulting yield strength was 78,000 psi, tensile strength 100,000 psi, elongation 20.0 pet in 2 in., and reduction of area 55.0 pet. Standard V-notch Charpy specimens were broken in a 217 ft-lb machine at a striking velocity of 16.8 fps. Energy absorption and fracture appearance of this material in the V-notch Charpy test are plotted as functions of temperature in Fig 1. After test, fractured halves of specimens appearing 0, 40, 80, and 100 pet fibrous (to the unaided eye) were electroplated with nickel, sectioned longitudinally (perpendicular to the notch at its midpoint), polished and etched with Cohen-Hurlich-Jacobson (C-H-J) reagent (picric acid plus Zephiran chloride in ethyl ether)4 or with Vilella reagent (1 pet picric plus 5 pct hydrochloric acid in ethyl alcohol).5 Fig 2 and 3 show cracks near the path of final fracture in the specimen rated 0 pct fibrous. Many of the cracks terminate at the boundaries of ferrite grains, some at boundaries of pre- existing austenite gzains. * A crack often starts near the end of another. Cracks within the same ferrite grains are parallel or approximately parallel in several cases. A large percentage of the cracks are branched. Fig 4 illustrated a group of cracks in the 40 pct fibrous specimen. Branching and parallelism are well marked. No more than three directions of crack have been observed on the polished surface in one ferrite grain. This is consistent with the evidence6 that brittle fracture of ferrite takes place on the cube face crystallographic planes: the {100} planes. The appearance of some cracks suggests that they have passed around a projecting corner of a second ferrite grain by going outside the plane of polish. In Fig 5 cracks in the 80 pet fibrous specimen may be observed. Some of

Jan 1, 1950

By R. W. Heckel, H. P. Cheskis, A. Lawley, M. R. Pinnel

THERE are discrepancies reported in the literature regarding the micro and macro stress-strain behavior of metals and alloys. In particular, Young's modulus and micro yield measurements often show significant variations depending upon the techniques employed.'-" The purpose of this note is to correlate measurements made with four techniques and to indicate where some of these discrepancies might arise. Allied use of these techniques can provide a complete and consistent characterization of micro and macro stress-strain behavior (over the strain range of 10-9 to 10--2 in. in.-') from a minimum number of samples. Techniques. The techniques employed for measuring stress-strain behavior involved the use of a) linear differential transformers, b) SR-4 strain gages, c) longitudinal resonance waves, and d) X-ray diffraction. Specimen geometries and preparations are summarized in Table I for each technique. Differential Transformer and Strain Measurements. An Instron universal testing machine, modified with an alignment device, was used to apply the load via parallel-jaw grips. The signal from the load cell was applied to the Y scale of a Moseley X-Y recorder (sensitivity of 10 lb load per in. chart). The elongation was monitored simultaneously with strain gages mounted on three sides of the rectangular specimen, and with two linear variable differential transformers (LVDT) mounted at 90 deg to one another on faces that also contained the strain gages, Fig. 1. The signal from one of the LVDT's was applied to the X scale of the recorder (sensitivity 40 µ in. elongation per in. chart) in order to trace a continuous load-elonga-tion curve. Concurrently, the strain on the same face (i.e., the face monitored by the LVDT) was recorded by the corresponding strain gage. A stress-strain curve was plotted from the load cell-strain gage data and was compared to the stress-strain curve (converted from load-elongation) plotted from the continuous load cell-LVDT trace. Identical Table I. Description of Specimens Used in the Present Study Material Dimerisions Preparation Condition 99.99 pct A1 tensile 318 by 3/16 by 3 in. as cast ingot; cut annealed specimen on diamond wheel 2024 A1 tensile 318 by 3/20 by 31/2 in. vacuum hot annealed specimen pressed sheets; cut on diamond wheel 99.99 pct Al 3116 by 3/16 by 2 in. cut from tensile prestrained dynamic modulus specimen after 10"* in. specimen test per in. 2024 A1 dynamic 3/20 by 3/20 by 2 in. vacuum hot annealed modulus specimen pressed sheets; cut on diamond wheel 2024 A1 X-ray gage section 112 by vacuum hot annealed specimens 1/4by1/20in. pressed sheets; cut on diamond wheel

Jan 1, 1970

By N. K. Chen, R. Maddin, K. T. Aust

Lattice rotations occurring on the tension and compression sides during the bending of molybdenum single crystals at room temperature were followed in detail. Observations were also made concerning crystallite rotations and slip traces. &apos;The results indicated the participation of (110) as slip planes and the<111>as slip directions. Crystallite fragmentation during bending was also noted. EVERAL investigations have been conducted on pure bending of face-centered cubic metals.&apos;-" Structural changes as a result of "bend-gliding," and the importance of bending and constraints during conditions of axial stressing, have been noted.&apos;," It was evident that the mechanism by which the bending deformation occurs is more complex than the case of simple shear. Studies of the bending of body-centered cubic metals from the aspect of the crystallographic mechanism appear to be lacking. Molybdenum single crystals therefore were subjected to deformation by bending in order to determine the reaction of the body-centered cubic lattice to bending stresses. It might be expected for the bending of single crystals that lattice rotation as represented by the axis of compression would proceed toward the pole of the active slip plane and that rotation of the tensile stress axis should indicate the slip direction.&apos; It was believed therefore that a study of the tension and compression sides of bent molybdenum single crystals should give data concerning the operative slip system. Specific problems which are pertinent to the overall picture of plastic deformation were also investigated, e.g., whether the constraints offered by pure bending give rise to the deformation band, and also the nature of the asterism occurring on the tension and compression sides during the stages of deformation. Experimental Procedure Eight single crystal specimens were grown from sintered molybdenum rods 143 in. diameter using the method described previously.6 The purity of this material was reported as 99.9 pct as described elsewhere.&apos; The specimens were % to 1/10 in. in diameter x 7 in. long, with single crystals approximately 1 to 2 in. in length occupying the entire center sections of each specimen. The specimens were elec-trolytically polished using an electrolyte of 300 cc methyl alcohol, 60 cc H2SO4, 130 cc HCl, and a current density of 4 amp per sq in. Each specimen was then loaded in a bending apparatus similar to that used by Yen and Hibbard,&apos; as shown in Fig. 1. The load was applied by means of a spring and screw arrangement through four ball-bearing surfaces set 1.5 in. apart. Either the inner two bearings or the outer two (A, B, Fig. 1) were attached to a movable steel plate (D) through which the load was transmitted. Since the apparatus was mounted on a track of the X-ray apparatus, the tension or compression side of the specimen could

Jan 1, 1954

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By R. E. Reed-Hill

A simple accurate graphical method for orienting fcc crystals using (111) slip traces on a single surface is described. Solutions placing the pole of the surface in a unit stereographic triangle are obtained using a Wulffnet, a (111) standard projection showing the four (111) planes, and a (111) standard projection ruled into unit stereogmphic triangles. The multiplicity of solutions is described in relation to this method. AN accurate, rapid single-surface technique for orienting fcc crystals, using (111) slip or twin traces, has been a matter of continuing interest, as evidenced by the periodic appearance of papers on this subject.&apos;-4 This note presents a new method possessing some advantages over those previously reported. It is an analog to the technique for hcp metals5 where the solution is based upon a stereographic rotation of the specimen surface on a (0002) standard projection that contains the planes of the possible features that might account for the observed traces. In the hexagonal solution, the axis of rotation is the basal-plane trace in the surface. In the fcc case, the axis of rotation is one of the observed ( 111) slip or twin traces. It has been observed that the solution is greatly facilitated if the indicated movements of the (111) traces during the rotation of the surface are plotted directly on a paper copy of a Wulff net as shown schematically in Fig. 1. The trace selected to represent the axis of rotation is assumed to fall at the north-south poles of the Wulff net. The directions of the other traces are then plotted as points at the proper angles around one-half of the basic circle of the net. The loci of points corresponding to the movements of these traces (directions) during a 90-deg rotation of the surface, about the polar axis of the net, are then easily and accurately drawn by following the appropriate small circles on the Wulff net. The solutions to the problem are obtained with the aid of a (111) standard projection of the (111) planes, see Fig. 2. This is normally a Xerox copy of a carefully drawn master made on high-quality tracing paper. The (111) standard projection is superimposed over the Wulff net and rotated about its center until the points of intersection of the loci of surface traces, drawn on the Wulff net, and the great circles representing the (111) traces, all lie along a common meridian of the Wulff net as demonstrated in Fig. 3. This latter great circle represents a possible position of the surface. The pole of this plane is then plotted on the (111) standard projection. Its location in a unit stereographic triangle may be readily obtained by superimposing (over the standard projection) another tracing paper (111) standard projection subdivided into unit stereographic triangles. The result of this last operation is shown in Fig. 4. MULTIPLICITY OF THE SOLUTIONS The maximum possible number of (111) traces on a single grain surface is four. Any one may be selected as the axis about which the surface is rotated. Corresponding to each such choice are three possible surface-pole orientations, related to each other by a simple 120-deg rotation about the pole of the (111) basic circle. This is a direct result of the threefold symmetry of the (111) standard projection. Since each of the four rotations will normally give a different set of three-pole positions, there are, accordingly, twelve possible solutions. Each of these twelve solutions places the surface pole in the same relative position in a stereographic triangle so that all are crystallo-graphically equivalent. Accordingly, only a single solution is required to obtain a basic orientation of the crystal. It should be noted, however, that the orientations obtained by reflecting* any of these twelve orien- *The reflected orientations may be obtained by a 90-deg rotation of the opposite sense to that shown in Fig. 1. This rotation places the correspond-ing trace loci in the lower hemisphere of the Wulff net rather than in the upper hemisphere. tations through the surface are also possible orientations that could account for the surface traces. Thus, a given set of four traces always corresponds to a pair of basic orientations related by reflection through the specimen surface. This ambiguity can only be re-

Jan 1, 1967

By R. L. Slobod, H. A. Blum

A semiquantitative method for measuring the wettability of reservoir rocks has been developed. These data are needed for reservoir analysis and for interpretation of laboratory displacement studies. The wettability of a core sample is measured by the contact angle for the system oil-water-solid. These contact angles are calculated from the displacement pressure (threshold pressure) obtained by use of the centrifuge, using first oil-water and second air-oil in the same core sample. This method is based on the assumption that the air-oil and oil-water interfaces occupy similar positions in the porous medium when desaturation of the wetting phase is initiated. The assumption is also made that the Contact angle for the air-oil-solid system which is close to zero in value does not change appreciably even when the contact angle for the oil-water-solid system experiences marked changes. "Apparent contact angles&apos;&apos; for five different solids ranging from 31" to 82" have been determined, and changes irr the "apparent contact angle" of a given sample with laboratory use from 33" to 53&apos; {lave been observed. INTRODUCTION Reservoir rocks vary in their wettability, 1,2,3,4 some being preferentially water wet while other are apparently preferentially oil wet. The degree of wettability, in theory, is measured quantitatively by the contact angle for the system solid-oil-water, hut in 1)practice this quantity is extremely difficult to determine." The need for obtaining some measure of this quantity has become obvious in recent years as a result of both laboratory. and field observations. Several reservoir.: such as the Bradford Sand in Pennsylvania and the Wilcox&apos; at Oklahoma City are reported to be oil wet. If these report:: correctly reflect the true nature of the surface of the rock in the ground, then these reservoirs probably will not perform as predicted on the basis of a water wet rock. In the laboratory many core samples have been Observed to be oil wet. These samples, while perhaps not correctly representing the reservoir, have markedly different properties from water wet rock. The location of the phases is different (oil is in contact with rock instead of water), and other quantities such as the connate water, the capillary pressure curve; residual oil. relative permeabilities. and the recovery of oil by water flooding are markedly affected by the value of the contact -4 A further complication observed in the laboratory is the chang-ing of the wettability of a rock specimen with use. such changes mean that repeat runs on the same core are not the duplicate tests desired, but represent new experiments on a more oil wet material. The changes in surface characteristics are sometimes so rapid that by the time an experiment requiring several days is completed, the results may not be representative of the core as originally described, The, rock material itself (Silica. carbonates. etc.), whell Clean and uncontaminated, is water wet. There seems b( : little evidence of the presence of oil wet minerals such as heavy metal sulfides. The oil wetness of reservoir samples, therefore, is believed to be caused by the accumulation of an adsorbed film in which the polar group of a large organic. molecule is adsorbed on the surface leaving the organic or hydrocarbon part of the molecule projecting out from the solid. Such a surface is much more readily wet 17" oil than by water. These considerations indicate the need for a method which will provide some measure of tile wettalbility (Contact(angle if possible) for reservoir rock ..samples) The method should be capable of (1.1 distinguishing between tile wettalility of dif. ferent formation,.. (2) detecting (change. ill wettalbility of a core with use. and (3) measuring the changes in Wettability which may be accomplished with cleaning operations. such as the use of sodium silicate for increasing water wrettalbility." A preliminary report on such a method is preseted below. not with the idea that this procedure alone will Solve the wettabil-ity problem. but rather that it may provide encouragement to

Jan 1, 1952