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By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By H. I. Aaronson

Isothermally formed plates of proeutectoid a, lengthen at approximately the rates predicted by the Zener-Hillert equation, indicating that their lengthening kinetics are controlled by the volume diffusion of chromium in the ß matrix. Solution annealing treatments in the vicinity of the transus introduce a second mode of transformation, in which the lengthening rate is at least 1.8 x 104 faster than predicted by this equation. Little or no volume diffusion appears to accompany the latter transformation. The Presence of oxygen is evidently a Prerequisite for the occurrence of this reaction. X HE effects of thermal history prior to the initiation of transformations which proceed by nucleation and diffusional growth are currently evoking considerable interest. The rate of nucleation (but not the rates of growth) of pearlitel and of bainite,2 and the over-all rates of aging reactions in Al-cu3 and Al-si4 alloys have been shown to be appreciably dependent upon thermal history in the solid-solution region"' or in the two-phase region prior to the onset of pre~ipitation.3,4 In none of these reactions, however, was the transformation mechanism changed by variations in the temperature-time path used to reach the reaction temperature. Preliminary experiments reported by M. K. McQuillan5,8 and a systematic investigation by Farrar and Margolin7 have disclosed that the transformation behavior of hypoeutectoid Ti-Cr alloys is considerably more sensitive to thermal history. Qualitative evidence strongly suggests that not only the rate of nucleation but also the rate of growth and even the mechanism of the ß — a reaction can undergo remarkable changes when a solution annealing treatment in the vicinity of the ß/a +ß, or transus temperature, is interposed between a high-temperature solution anneal (conventionallq at 1000°C) and the isothermal reaction treatment. The present investigation was undertaken in an attempt to ascertain the nature and origin of these effects. Study of the changes in the kinetics and morphology of the ß - a, reaction produced by varialtions in thermal history was the primary means employed for this purpose. EXPERIMENTAL PROCEDURE The compositions of the alloys used in this in~esti~ation are given in Table I. These alloys were homogenized for 5 days at 1050° C in evacuated (2 x 10 -5 mm of Hg), zirconium-gettered fused quartz capsules. The capsules themselves were enclosed in a porcelain chamber evacuated with a mechanical pump during the homogenization anneals. Upon completion of homogenization, the alloys were cooled to room temperature and then reheated to 550°C for 3 1/2 days in order to transform the alloys to a finely divided mixture of a and TiCr2, and thus provide an approximately constant initial mi-crostructure. Individual specimens were sealed in evacuated and internally gettered Vycor capsules and heat treated as previously described.8,9 EXPERIMENTAL RESULTS Ti-10.64 Pet Cr. This investigation was largely performed on the 0.64 pet Cr alloy. The "base"

Jan 1, 1962

By D. W. Levinson, L. F. Mondolfo, N. A. Gjostein

MANY investigations are reported in the literature on the age hardening of Al-Mg-Zn alloys but most of them are concerned mainly with mechanical property changes. The present investigation was started to determine the structural changes in an AlMgZn alloy. The alloy composition was chosen in the existing phase diagram" so as to lie on the quasi-binary section Al-(AlZn)Mg Actually, it was found that the diagram as published was inexact at the lower temperatures and that the phase in equilibrium with aluminum at the lower temperatures is not the ternary compound. Technique The alloy used for the investigation was prepared from high purity materials and the resulting composition as determined by chemical and spectro-graphic analysis was: Zn, 6.17 pct; Mg, 2.13 pct; CU, 0.03 pct; Si, 0.009 pct; Fe, 0.005 pct; and the remainder, aluminum. An ingot -in. thick was cast, homogenized, hot and cold-rolled to strip 0.064-in. thick for dilato-metric and powder work, and to foil 0.005-in. thick for single crystal work. Solution treatment temperature for all specimens was 475°±5°C for periods of at least 1 hr, either in air furnaces or lead baths. Aging was done in oil or Pb-Bi baths controlled to within ±3°C. The aging was investigated at the following temperatures: room (30°), 130°, ZOO0, 260°, and 300°C. For the dilatometric study, the length changes were measured continuously, at temperature, using strips of alloy 10 in. long, shaped as channels to eliminate undesirable deflection due to bending. To compensate for thermal expansion and contraction due to the variations in the temperature of the aging baths, the dilatometers were built of the same alloy as the one being tested, with the same shape and size, but with material fully annealed. Gages on which 0.0005 in. could be read and 0.0001 in. estimated were used to measure the dilation. Length changes were also measured at room temperature. Strips approximately 10 in. long were solution-treated, quenched, and measured in a supermicrome-ter in which 0.0001 in. could be read and 0.00001 in. estimated. The specimens were immediately aged for a given time, remeasured, and then the cycle was repeated, including the solution treatment. The error of measurement with this technique was somewhat larger, but the results confirmed those obtained by continuous measurements. The sheet used for the dilatometric work was checked to determine grain orientation. Both X-rays and etching methods revealed a rather coarse grain size but only a negligible amount of preferred orientation. Thus, volume changes calculated from length changes are not invalidated by preferential orientation effects. Pieces of the sheet used for the dilatometric work were also used for the metal -lographic work. Filings for the powder X-ray study were produced from a homogenized piece of sheet. These filings were magnetically purged of iron, screened to 200 mesh, sealed in a Pyrex tube containing an argon atmosphere, and solution-treated. When quenching, the glass tube was broken, so that the powder dropped directly into cold water. After drying with alcohol, the powder was sealed into capillary tubes containing an argon atmosphere and then aged for the required times. In spite of all these precautions the three strongest lines of a( Al2o) appeared in all patterns, and were used as internal standards. By the use of these standards, accurate corrections for film shrinkage were obtained. For the back reflection patterns, annealed nickel powder was mixed with the specimen to act as internal standard. A preliminary investigation was made in small (57.3 mm diam) powder cameras. From these patterns the changes which took place in the solid-

Jan 1, 1957

By R. I. Jaffee, C. M. Craighead, G. A. Lenning

THERE has been considerable discussion among A metallurgists and others interested in the development of titanium alloys as to the nature of the fine line markings which appear in the microstruc-tures of unalloyed titanium and a titanium alloys. These markings have been variously called x phase, etching pits, and twins. Figs. 1 to 3 show typical examples of the line markings as they appear, respectively, in high purity iodide titanium, commercial purity titanium rod, and a high purity a alloy containing 0.2 pct N. The commercial purity titanium sample, shown in Fig. 2, contains both line markings and some spheroidal retained-ß phase. The ß phase seen in this micrograph should not be confused with the line marking, since it originates from the iron present as an impurity in the sponge metal. It will be noted that the line markings seem to have a definite orientation pattern with respect to the grains and in titanium noticeably resemble the precipitation occurring in artificially aged high purity Al-Cu alloys. This similarity led to the hypothesis that the line markings observed in titanium and a titanium alloys resulted from precipitation of some unknown phase. With the work of Hägg1 and McQuillan2 as background, there was little reason to suspect hydrogen of being responsible for the line markings. Hagg reported that up to 33 atomic pct H was soluble in a titanium, and McQuillan reported an a solubility of up to 8 atomic pct. Furthermore, McQuillan examined metallographically a 5.1 atomic pct H alloy quenched from 300°C and stated that the structure appeared to be a single-phase a solid solution. Line markings have been observed frequently and were first noted by Jaffee and Campbell3 in 1949. They did not observe them in vacuum-annealed titanium and a Ti-O and Ti-N alloys, but did observe them in Ti-H alloys containing 0.25, 0.5, and 1 atomic pct H. They stated that it was doubtful that the markings were a second phase based on hydrogen, because 1 atomic pct was far from the accepted solid solubility of hydrogen in titanium. Finlay, Resketo, and Vordahl,4 in 1950, concluded that the markings were a true second phase as a result of observations on their etching characteristics. Anderson5 Commenting on these markings in titanium was inclined to associate them with hydrogen, but was loath to call them titanium hydride, because of the reported high solubility of hydrogen. Work at Battelle Memorial Institute for the Navy Bureau of Aeronautics," done concurrently with the work described in this paper, provided information on the experiment converse to that described by Jaffee and Campbell in 1949. This work showed that the amount of line markings in unalloyed titanium could be decreased by vacuum annealing at elevated temperature. It was suggested that this was the result of removal of hydrogen; previously, the data of Jaffee and Campbell9 howed that the markings appeared when hydrogen was added. Recent work at Battelle for the Ordnance Corps, Department of the Army, which is described here, now establishes the identity of the markings as a titanium hydride phase. A sample of high-purity titanium rod 1/4 in. diam, 0.009±0.001 wt pct H (0.43 atomic pct), Fig. 1, was resistance heated in a 0.05 micron vacuum for 41/2 hr at 1500°C. During the early states of heating, the pressure increased to 150 microns, indicating that gases were being evolved. After cooling in vacuum, the iodide titanium rod was analyzed for hydrogen. Vacuum-fusion analysis showed 0.0006 ±0.0003 wt pct H (0.03 atomic pct) to be present.* Metallographic examination of the vacuum-annealed rod showed only a transformed ß structure. There was no evidence of fine line markings, Fig. 4. A section of this vacuum-annealed rod was cold rolled to 0.040 in. thick sheet and annealed for 1 hr

Jan 1, 1953

By Shiro Ban-ya, John Chipman

The effects of many alloying eletnents on the acticity coefficient of sulfur in liquid iron have-been studied by the equilibriutn in the reaction Sfin Fe) + Hz = HzS at 1550°C'. Results are expressed in terms of a concentration variable for a nonmetallic or for a substitutional metallic solute. Activity coefficient of sulfur, defined as increased by B, Al, C, Si, Ge, Sn, P, As, Sb, Mo, W, Co, and PI. It is decreased by Cu,Au, Ti. Zr, V, h'b, Ta, Cr, ,23n, and Ni. Irulues oj. the interaction coejficient 0i = 6 In are labulated. The same interactions are expressed also in terms of atom fraction and of weight percent. The thermodynamic properties of sulfur in liquid iron have been fairly well established. Our recent paper1 reported new determinations of activity coefficient up an atom fraction of 0.12 and equations based on a careful review of all published data. The effects of alloying elements on the activity of sulfur have been studied by several investigators,2"11 especially by Morris and Williams for silicon,' by Morris and Buehl for carbon,~ and by Sherman and Chipman for manganese. phosphorus, and al~minum.~ However, the effects of some important alloying elements remain to be determined. The purpose of this investigation was to determine the effects of many alloying elements on the activity of sulfur in Fe-S-j ternary systems. EXPERIMENTAL METHOD This study was based on experimental determination of equilibrium in the reaction at 1550°C: The same apparatus and procedure as described in our previous paper have been retained, and the same corrections were applied for dissociation of H2S. The alumina crucibles used in the experiments consisted of four separate compartments. In a given experimental run. kach of three alumina crucibles held four different samples of about 3 g each which reached equilibrium in the same gas atmosphere and temperature. The charges were made up of electrolytic iron, pure iron sulfide, and desired alloying elements, which were pure metal or master alloys made in the laboratory. The weighed samples were held for 4 to 12 hr in the prepared atmosphere at 1550°C. They were then low- ered to be cooled as quickly as possible. The quenched metal beads were crushed to avoid the errors of segregation in the ingot. The sulfur content was determined gravimetrically and alloy content by appropriate chemical analysis. CALCULATIONS The apparent equilibrium constants of Eq. [I] are expressed as follows from the corrected gas ratios and sulfur concentrations: The term K" is the observed equilibrium constant in any given ternary solution, K' is the value for the Fe-S binary solution. and the limiting value of K' in the infinitely dilute solution is designated by K, which is the true equilibrium constant in Eq. [I]. In the thermodynamic treatment of nonmetallic elements in a metallic solution, it has been suggested1' that the lattice ratio has certain advantages over other variables to express the concentration of solute. In interstitial solid solutions the lattice ratio zj is proportional to the ratio of filled interstitial sites to those which remain unfilled. The equations derived for the activity of the solute using zj as the concentration variable are found also to be applicable to liquid solutions containing nonmetallic solutes when the nonmetal is treated as if it were interstitial. For this purpose we adopt the following definitions: The quantity vj which is negative for interstitial solutes is taken as -1 for nonmetallic and +1 for metallic solutes. For purposes of calculation however ; j may be assigned a value which results in a linear relation such as shown in Figs. 1 to 15. The activity coefficient of sulfur, Qs, and equilibrium constant. K(z). are defined as follows: According to a Taylor series expansion. the logarithm of the activity coefficient of sulfur in Fe-S-j ternary system is: However, the value of 6 In */6zi remains constant through a broad range of dilute solutions and the terms of higher order are negligibly small. As a consequence, Eq. [6] is simplified as follows:

Jan 1, 1970

By D. Kunstelj, M. Stubicar, A. Tonejc, A. Bonefacic

A. Bonefafcic, D. Kunsfeli, M. Stubicar, and A. Tonejc The present communication is concerned with the variation of the texture in aluminum wires with die angle and temperature, at constant speed of extrusion. Experiments were carried out concurrently on refined samples, with a stated purity of 99.997 pct pure A1 and commercial samples of 99.5 pct Al. Ingots of refined aluminum samples were machined to 30-mm-diam by 150-mm-long billets. These billets were transformed to 5-mm-diam wires by drawing. The final form, suitable for examination, was obtained by extrusion through conical-face dies with a 1-mm hole diam and extrusion ratio 5:l in diam. The initial form of the commercial aluminum samples was drawn wire 5 mm in diam. These samples showed a poorly defined texture with (111) as a major and (001) as a minor component. A similar defined texture appeared in the refined aluminum samples after drawing to 5 mm diam. Conical-face dies with different angles (defined by the axis and the generating line of the cone) were used in our experiments. The values of the angles were 27, 35, 45, 57, 63, and 90 deg. The extrusion container was fitted with a heating element and controller permitting temperatures up to 600°C to be maintained within i5"C. Extrusion was performed at 250°, 300°, 350°, 400°, and 500°C at constant speed (approximately 1 mm per sec) and constant die reduction. The extrusion product was a wire 1 mm in diam and approximately 20 cm long. In order to remove the surface layer with the "conical" texture and to reduce the absorption by the X-ray examination of the samples, the extruded wire was etched to 0.22 mm in diam. Experiments were performed in the middle sections of the 20-cm-long wires. In addition to the die of l-mm hole diam, dies with a 1.5-, 0.7-, 0.6-, 0.5-, and 0.4-mm hole diam and 63-deg die angle were constructed. In our experiments we did not find in these ranges any important difference concerning the texture of the extruded wires and we continued our work solely on the 1.0-mm die. The diffracted X-rays (Cu K radiation) were recorded photographically. Diffracted intensities were measured on the (111) reflection with a microphotometer. The relative amounts of texture components were determined from the areas under the diffracted maxima. We found the texture of extruded aluminum wires to be strongly influenced not only by the temperature of extrusion and the purity of the sample but also by the form of the die. It is generally admitted that cold-drawn aluminum wires have mainly a (111) texture with a small amount of (001) component, Table I of Ref. 1. In our experiments with wires extruded in conditions represented by Fig. 1, in some cases a single (001) texture was obtained. If these wires were drawn repeatedly at room temperature, X-ray measurements revealed a duplex (001)-(111) fiber texture. Further drawings increased the (111) and decreased the (001) texture component. In Fig. 1 the percentage of material oriented with (001) parallel to the extrusion direction is represented as a function of the temperature and the die angle (a), for commercial and refined aluminum samples, respectively. From these diagrams we may draw the following conclusions. The slope of the die (a) influenced more strongly the texture at the lower rather than the higher temperatures. Again, a stronger influence was found in the case of the commercial in comparison with refined aluminum samples. In the case of the commercial aluminum samples the amount of material with (001) texture increases with increasing wire temperature in an approximately linear manner. This effect is less pronounced in the pure aluminum samples, with the exception of the die with a = 45 deg. In this case the (001) texture decreases with increasing temperature, as shown in Fig. 1. Component (001) is more pronounced in higher-purity aluminum samples. Our experiments led to the conclusion that both (001) and (111) components are essentially stable in extruded aluminum wires. As we obtained a single (001) texture starting with a sample of drawn wire in which the (001) component was very weak, our experiments revealed that the (001) component is not a remnant of the initial texture; this is in disagreement with the findings of Vandermeer and McHargue.1 We gratefully acknowledge discussions with Professor M. Paic. 1 R. A. Vandermeer and C. J. McHargue: Trans. 7MS-AME, 1964, vol. 230, p. 667.

Jan 1, 1969

By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968

By A. L. Field, P. H. Royster

Bureau of Mines Technical Paper 189 consists of a record of the scientific data obtained in the iron blast-furnace slag investigation which is reported in Technical Paper 187, "Slag Viscosity Tables for Blastfurnace Work." It includes a description of the method of preparing the synthetic melts, construction of an improved electric furnace, and refinements in laboratory methods of measurement. Only the general features of the work and the conclusions drawn from the experimental data can be given attention here. Silicates in the Liquid State In the manufacture of refractories, Portland cement, glass, and porcelain, and in pyrometallurgical operations, importance attaches to the behavior of-silicate compounds at temperatures beyond the range of common experience. This field of research has not been investigated as carefully as its scientific and industrial importance would seem to warrant. Probably the most important of the unsolved problems in the chernistry of silicates is the question of their stability in the liquid state. That little progress toward the solution of this problem has been made is not strange if there be borne in mind the difficulties attending experiments made at temperatures at which silicates become fluid, and the comparatively short time since it became possible to measure these temperatures. On the other 'hand, considerable progress has been made in the study of the compounds in the solid state because of the directness and simplicity of methods of optical examination. Important advances have been made by the Geophysical Laboratory at Washington in recent years. An extended study has been made there of saturated solutions representing a considerable number of binary and ternary systems of the more common refractory oxides. The methods

Jan 1, 1918

By J. S. Kirkaldy, D. H. Weichert, G. R. Purdy

Two-phase diffusion couples have been used to simulate the growth of proeutectoid ferrite in ternary Fe-C-Mn austenites. It has been shown, theoretically and expermentally, that the results fall into two classes: a high-super saturation class in which the major role of manganese additions is to influence the boundary conditions for carbon diffusion; and a low-supersaturation class in which the partition of manganese is required. In the latter case, a drastic inhibition of the reaction rate is to be expected. As an aid to the kinetic analysis, a portion of the iron-rich comer of the Fe-C-Mn constitution diagvam has been determined. The conclusions drawn from this work have a direct bearing on the kinetics of the grain boundary ferrite precipitation reaction and thus yield insight into the manner in which alloying elements can influence the rate of austenite-decomposition reactions. THE role of alloying elements in the austenite-decomposition reactions has provoked considerable interest, since it is apparent that an understanding of this phenomenon will yield insight into the harden-ability problem. In the present investigation, attention is focused upon the proeutectoid-ferrite transformation in the system Fe-C-Mn, and upon the manner in which manganese additions affect the growth rate of ferrite. When hypoeutectoid austenite is supersaturated, the ferrite first formed usually exhibits two distinct types of morphology. At low super saturations, grain boundary layers grow into the austenite grains with an approximately planar interface, and usually possess at least one incoherent phase boundary. At high supersaturations, Widmanstiitten plates appear, which bear an orientation relationship' to the parent austenite. In this case, there is a chance of partial lattice matching along the sides of the plates and an attendant semicoherent interface structure. Purdy and Kirkaldy2 have used a two-phase binary Fe-C diffusion couple to demonstrate that carbon volume diffusion controls the incoherent reaction, while Rouze and rube,' using thermionic-emission microscopy, have shown that the thickening of Widmanstatten ferrite plates is appreciably slower than expected for carbon-diffusion control. This suggests that the plates are bounded by partially coherent, low-mobility interfaces. The redistribution of alloying elements during transformation has been the object of studies by Aaronson4 and owmman,5 who have shown that no alloy partition occurs during ferrite precipitation in the systems Fe-C-Cr and Fe-C-Mo, respectively. More recently, Aaronson et al.6 have shown that some manganese partition occurs at low super-saturations in the system Fe-C-Mn, but that no partition occurs at higher super saturations. Pickle-simer et al.7 observed that no manganese partition occurred during the early stages of the pearlite transformation in a manganese steel, and concluded that volume diffusion of the alloying element is not the rate-deter mining factor. The diffusion coefficients pertinent to this investigation have been measured by Wells, Batz, and Mehl8 (carbon in austenite), R. P. smith9 (carbon in ferrite), Wells and Mehl 10 (manganese in austenite), and Kirkaldy and Purdy11 (diffusion of carbon on a manganese gradient in austenite). Kurdjumov 12 has shown that the diffusivity of substitutional elements in ternary austenites up-quenched from martensite may be greatly enhanced, due, apparently, to the presence of a persistent defect structure. The recent work of Krauss 19 showing high densities of tangled dislocations in reversed Fe-Ni martensite is in agreement with this conception. THEORETICAL Diffusion in ternary or higher-order systems may be described with the aid of Onsager's extenbion of Fick's first law,14 in which the flux of each of the n components is assumed to be a linear function of all concentration gradients:

Jan 1, 1964

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

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks' and to the precipitation of second phase particles,2'3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these '(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

By B. S. Hickman

Using primarily quantitative single crystal X-ray techniques studies have been made of the precipitation of the metastable w phase in alloys of titanium with Mo, Mn, Fe, Cr, and Nb. It is shown that, in agreement with earlier work on the Ti-V system, the composition of the w phase during aging approaches a constant; the value varies from one system to another in a systematic manner with the electron concentmtion. Results relevant to the mechanism of w precipitation during quenching and during aging are presented and discussed. Results are presented to confirm that the w phase is coherent and the nzorphology of the Necipitates is described and discussed. PRECIPITATION of the metastable w phase in alloys of titanium is of interest because of its severe embrittling effect and also because of the enhancement of the superconducting properties which accompanies precipitation.1 The general features of w phase precipitation have been discussed by cuillan and by Bagaratskii et d3 The work described in this paper forms part of a general study of w phase precipitation which was undertaken to elucidate various unknown or controversial features of the process, namely: i) What is the mechanism of formation of the phase ii) How does its composition, morphology, volume fraction, and particle size vary with the type and content of the alloying element and with the heat treatment conditions? iii) What is the relation between the w phase and the equilibrium a phase? In a previous paper4 the results of a detailed study of w phase in Ti-V alloys were presented. It was shown that: U During aging the composition of the w phase approached a saturation value of 13.5 to 14.0 at. pct V. ii) w precipitated as cube shaped particles and once precipitation was complete, particle coarsening did not occur. iii) a phase formed initially by direct conversion of w-phase precipitates. In this paper similar measurements are reported on Ti-Mo alloys and some more limited data given on the Ti-Cr, Ti-Fe, Ti-Mn, and Ti-Nb systems. The results i.1 the six systems are then compared. It has been shown previously by electron microscopy that the w precipitates as ellipsoids in both the Ti-Nb system,&apos; and in i-o.&apos; Blackburn and williamsz3 have reported the precipitates in Ti-Fe, Ti-Cr, and Ti-Mn are cubic, i.e., similar to the Ti-V system.476 EXPERIMENTAL METHODS 1) Specimen Preparation. Samples of the compositions shown in Table I were prepared by arc melting. High purity electron beam zone refined titanium (Materials Research Corporation Grade I—total impurity content =250 ppm) was used; the other source materials are given in the table. A commercial Ti-8 wt pct Mn alloy was used for studies of this system. After homogenization the materials were rolled or cut into strip approximately 1/4 in. by 2 in.; the strip was then heated at temperatures of 1200" to 1300°C for several hours by passage of a direct current through the strip in an ultra high vacuum system (<10-torr) and then quenched by admitting high purity helium and switching off the current. This treatment resulted in crystals up to 2 in. by 2 in. by A in., almost all of which had a [100] direction nearly perpendicular to the plane of the strip. The crystals were cut from the strip by spark machining and their composition checked by lattice parameter measurements supported by chemical analysis. 2) X-Ray Diffraction Methods. Lattice parameter measurements were made using a modification of the single crystal spectrometer described by ond. In this technique the crystal angles for reflection on either side of a highly collimated primary beam are measured. Generally the 400 CuK, or the 400 CuKp reflections of the bcc lattice were used. In the as-quenched crystals a precision of 1 in 105 was obtained, but due to line broadening the parameters in aged materials could only be measured to 1 in lo4. This accuracy was, however, quite adequate for the purposes of these experiments and enabled the composition of the p phase to be obtained to 10.1 pct in all systems except Ti-Nb where the lattice parameter change with composition is very small. The precipitation and growth of the w phase was examined using a single crystal goniometer attached to a Phillips diffractometer. The relative intensities and line shapes of b-phase and w-phase reflections

Jan 1, 1970

By A. S. Yue, A. G. Guy

A study was made of the effects of a prolonged flux of zinc atoms through the a solid solution of zinc in copper. The experimental arrangement consisted essentially of a copper disk about 0.01 in. thick, at one of whose surfaces a gaseous atmosphere containing zinc atoms was maintained, and at the other surface a gaseous atmosphere with a minimum of zinc atoms was maintained. During prolonged theothersurfaceexposure at high temperatures the zinc content of the copper disk gradually built up to the steady-state concentration distribution and then remained at this value. The concentration-distribution curves for various conditions were determined by chemical analyses. The results showed that the condition of steady-state diffusion was achieved. The diffusion coefficients calculated from the experimental data, although not of high precision, agreed with the values obtained by other workers using unsteady-state methods. Relatively slight porosity developed in the specimens in the course of diffusion. A LTHOUGH most diffusion studies have been made under unsteady-state conditions, it is known&apos; that the steady-state method is often superior with respect to the directness and accuracy of interpretation of the data. Steady-state diffusion of gases through metal diaphragms is well known. Also, Harris&apos; and Smith" have used the steady-state method in studying the diffusion of carbon in aus-tenite. The accepted mechanism in this system involves the motion of the interstitial carbon atoms in the rigid framework of the lattice of iron atoms. Thus, there is little difficulty in visualizing the steady flow of the small carbon atoms through the austenite. The situation in substitutional diffusion is quite different. Here the atoms are comparable in size, and it is not evident how a steady flow of one of the atoms through the solid solution might be achieved. At the time the present research was started, it was known that a previous exploratory attempt to produce steady-state diffusion in a substitutional alloy, the Au-Ag system,&apos; had been unsuccessful and had indicated that perhaps there were basic difficulties that could not be ovei-come. Therefore, the present research began as a study of the effect of a prolonged flux of metal atoms through a substitutional solid solution. Eventua.lly, it was possible to produce actual steady-state diffusion in the system chosen for study, the a Cu-Zn alloys. Experimental Procedure The aim in the experiments was to maintain a high zinc content, about 30 pet, at one surface of a copper sheet, and to maintain a low zinc content, near 0 pet, at the opposite surface. The zinc would then diffuse into and through the copper, first building up to the steady-state concentration distribution and then maintaining this distribution. The three types of specimens that were used are shown in Fig. 1. In type A specimens the copper disk through which diffusion occurred was welded to the top of a cylindrical molybdenum tube, the bottom of which also was sealed by welding. At the diffusion temperature the brass chips in the molybdenum container were the source of the zinc vapor which maintained the lower surface of the copper disk at 30 pet Zn. The upper surface was maintained at 0 pet Zn by the vacuum in which type A, and also type B, specimens were diffused. Since the molybdenum container was impervious to zinc vapor, it was intended that the only path of escape for the vapor from the brass chips would be through the thin copper diffusion disk. However, it was found that small leaks often developed at the welded joints during the diffusion treatment, and in most specimens some of the zinc was lost in this manner. Although even small losses of this kind were a serious handicap in attempting to determine the flux through the disk, they did not prevent the maintenance of satisfactory boundary conditions for the attainment of the steady-state condition. Type B specimens differed from type A in having a weight of about 300 g supported on the copper disk by 15 to 20 short quartz rods. This change was made when it was observed that the copper disk was being bowed upward by the difference in the pressures acting on its two surfaces. Since the grain-boundary cracking which occurred in the bowed specimens could be attributed largely to the accompanying creep,3 it was desirable to minimize this effect. The counterweight was effective in significantly decreasing both bowing of the disk and cracking at grain boundaries. Type C specimens differed considerably from the others in that the low-zinc atmosphere at one sur-

Jan 1, 1959

By S. R. Goodman, Hsun Hu, R. S. Cline

The quenching technique has been used to study phase relations in the composition area 2FeO.SiO2-FeO-SiO2-MnO.Si02-ZMnO.SiO2 of the system iron oxide-manganese oxide-silica under strongly reducing conditions such as exist in a gas mixture consisting of equul parts of carbon dioxide and hydrogen. Liquidus and solidus temperatures of most mixtures in the composition area studied are in the range of 1173° to 1345°C. EQUILIBRIUM relations existing among the oxides of iron, manganese, and silicon are of particular interest in two areas of steelmaking: slags and ingot inclusions. Mixtures of these oxides represent about 90 pct of the slag in the acid steelmaking process, and so dominate the chemistry of the whole refining process. These constituents also play an important role in the early slags existing at the time of the "lime boil" in the basic open hearth process. If these slags are liquid, they "wet" the lumps of lime rising from the bottom of the bath, and react with them. A liquid slag rich in CaO is then formed at the very beginning of the refining. Because the temperature is still low, all conditions for a good dephosphoriza-tion are fulfilled at this stage of the operation. Metal deoxidized with ferromanganese or silico-manganese is likely to contain, as inclusions, phases made up from among the oxides of iron, manganese, and silicon. A knowledge of stability relations existing among the phases present in this system, therefore, enables one to predict the hardness of the inclusions encountered. Moreover, because the shape of the inclusions in steel has a profound influence on the physical properties of the metal, it is important to establish whether or not the oxidic material is present as liquid or crystalline phases during heating and rolling of the steel (-1150 to 1350°C). A knowledge of melting relations in synthetic mixtures of iron oxide, manganese oxide, and silica will give a clue to these problems. Methods for determining such relations and the results obtained are described iln this paper. I) PREVIOUS WORK A number cf previous studies have dealt with the three "binary"* systems bounding the system iron oxide-mangar,.ese oxide-silica. The system iron oxide-silica was studied by Bowen and shairerl in 1932. Their data were obtained by equilibration of mixtures in contact with metallic iron. Phase relations for the system iron oxide-silica ill atmospheres of different oxygen pressures car1 be derived from data on the system FeO-Fe2O3-SiO2 as determined by Muan.2 The diagram shown iri Fig. l is a section of this system in an atmosphere of CO2 and H2 in ratio 1:l. The system manganese oxide-silica has also been the subject of several investigations. Most of the early studies suffered from a lack of proper control of the atmosphere under which the equilibrations were carried mt. Phase diagrams for the system at two well defined levels of oxygen pressures have been determined recently. Glasser3 determined stability relations in an atmosphere consisting of carbon dioxide and hydrogen in ratio 5:1, diagram Fig. 2, and Muan4 studied phase relations in the system in air.

Jan 1, 1962

By S. K. Mitra

A refinement of the Seeger model for intersection process is investigated which is in better agreement with experimental observations than the original. It is shown that, in single crystals, the strain hardening in Stage II is mainly due to the short-mnge interactions when intersection is the rate-controlling process. It is also demonstrated that the creep curves, as predicted by this theory, are in good agreement with the experimental observations. MOTT: Cottrell? and Seeger have developed an approximate theory for plastic deformation of single crystals over the range of variables where the strain rate is controlled by the rate of intersection of dislocations. Although it is now generally agreed that the low temperature deformation of many pure metals is controlled by the intersection mechanism, various dictates of the over-simplified Seeger model are not in good agreement with all the experimental facts. It is the purpose of this paper to reveal that by appropriate extensions of the Seeger model, particularly those suggested by Basinski: a much more reliable theory results. The refined model to be presented here will be shown to account, in a satisfactory way, for the effect of stress, temperature, and strain on the creep rate under constant stress and for the effect of temperature and strain on the flow stress in constant strain-rate tests. EXPERIMENTAL METHOD To Check the theoretical deductions, both creep and tension tests were conducted on single crystals of high-purity Al (99.994 pct Al) so oriented that both the active slip plane and the Burger&apos;s vector of the operative dislocations on that plane made angles of about 45 deg to the tension axis. Single crystals of aluminum (5/8 in. by 1/10 in. by 8 in.) were grown in a graphite mold under an inert atmosphere using the Bridgman method. The chemical composition of the aluminum is given in Table I. A common seed was used for all crystals and their orientation is shown in Fig 3. The extensometry consisted of two differential transformers with matched outputs mounted so as to measure the extension in a 2 in. gage length. The amplified difference in output of the two transformers was recorded by a potentiometer. The amplification was calibrated before each run so that one chart division of the recording potentiometer indicated a 105 shear strain on the specimen. Stresses were measured to the nearest 1 x l04 dynes per sq cm. ACTIVATION VOLUME The concept of Basinski that the activation volume is not constant but is a function of the force that aids thermal fluctuation in effecting the cutting of dislocations will be adopted in this section. The force acting due to an applied shear stress on the dislocation being intersected is where L is the mean spacing between the forest dislocations, is the Burger&apos;s vector and T is the back stress. A detailed discussion about the origin of back stress will be taken up later in this report. As shown by Basinski, the activation energy, U, that must be supplied by a thermal fluctuation in order to effect intersection, is equal to where x is the distance through which the dislocation must be translated for complete intersection, and Fm is the maximum force encountered in intersection. When the applied stress is decreased abrupt ly F also decreases and the activation energy increases correspondingly as documented in Eqs. [ 1 ] and [2]. The Seeger equation for the strain rate when the deformation is controlled by rate of intersection of where the shear strain rate (per sec) N = the number of points per unit vol at which intersection can take place

Jan 1, 1962

By A. E. Dwight, P. A. Beck

A search was made for ordered phases of AB3 composition in various combinations of Ti- and V-group elements with CO-and Ni-group elements. Three new TiNi3-type phases ZrPd3, HfPd3, and HfPt3 were found. In addition, twelve new Cu3Au-type phases TiRh3, Tilr3, ZrRh3, Zrlr3, HfRh3, Hflr3, VRh3, VIr3, CbRh3, Cblr3, TaRh3, and TaIr3 were also found. The lattice contraction for all three structures considered increases with increasing relative size of the A atom, suggesting that it is mostly the A atom that cont~acts. It was noted that, for the same radius ratio the lattice contraction is larger when the A atom is Ti than if it is Cb OY Ta. It is well known that elements or disordered solid solutions, which have structures with spherical close-packing, may be described in terms of various stacking schemes of close-packed layers. Stacking of the type abab corresponds to the hexagonal close-packed structure, and stacking of the type abcabc corresponds to the face-centered-cubic structure. In binary alloys of the first, second, and third long period transition elements various AB3 phases occur with close-packed ordered structures. It was observed that these ordered structures also may be described by suitable stacking of close-packed ordered layers, Fig. 1, as first shown by Laves and Wallbaum for TiNi3.&apos; It is clear that the units of translation in such a close-packed layer consist of four atoms, one of which (black circle) is atom A and the three others (empty circles) are atoms B. Because of the alternation of A and B atoms in every second row of each layer, the unit-cell dimension in the layer is equal to the sum of the diameters of atoms A and B: a0 = 2(rA + rB). Stacking of such layers in the sequence abab results in a hexagonal close-packed structure of the MgCd, type. The unit-cell dimension in the basal plane is approximately double of that for the disordered hexagonal close-packed structure, but in the direction of the hexagonal axis it is about the same, so that 2co/uo = 1.63 in case of spherical close-packing. Ordered hexagonal close-packed structures of this type were found to occur in MoCo3,2 WCo3,, and UPt, .4 When the ordered layers shown in Fig. 1 are stacked according to the scheme abcabc, the resulting ordered structure is of the AuCu, type (cubic). Structures of this type were found to occur in TiPt3,5 CrPt,,&apos; CrIr,,&apos; and URu, .4 Finally, the stacking scheme abacabac of the same ordered layers results in a hexagonal close-packed structure of the TiNi3 type.&apos; In this case, the unit-cell dimension is doubled not only in the basal plane, but also in the direction of the hexagonal axis, so that co/ao = 1.63. Structures of this type were found to occur also in TiPd3,5 ZrPt,," and UPd,.4

Jan 1, 1960

By H. E. Cline, D. F. Stein

A fine lamellar structure with interlamellar spacings ranging from 0.I to 3.7 was Woduced by high-speed directional solidification and used to study the interaction of dislocations with an array of bimetallic bound-am.es. The tensile flow properties were measured at elevated temperatures and the results interpreted in terms of an image force model. As the width of the plates decreases the strength increases according to a Hall-Petch relation, suggesting pile -ups. Considerable strengthening was also observed at elevated temperatures. In recent years composites containing a strong but brittle phase and a ductile but weak phase have been studied extensively in the search for a high-strength material with adequate ductility.&apos; However, the strength of these composites has been limited to a volumetric average of the strengths of the component phases. In this paper we will show that a composite made by directional solidification of a Cu-Ag eutectic has strength properties that substantially exceed the strength of either of the metals in the composite, and an explanation for this increased strength will be presented. The Cu-Ag eutectic is a near ideal material to study for several reasons. The eutectic structure is made up of alternate plates of silver-rich and copper-rich phases with the same crystal structure.2&apos;3 In addition, the mechanical and elastic properties of silver4 and copper5 are known over a wide range of temperatures and the eutectic microstructure is stable to nearly the melting point.6&apos;7 Therefore, the properties of the eu-tectic are readily comparable to various theories involving the mechanical properties of copper and silver. The experiments consisted of producing directionally solidified Ag-Cu eutectic material, determining the structure and performing tensile tests at different temperatures and strain rates. EXPERIMENTAL A) Solidification and structure. A cylindrical ingot 2.2 cm in diam and 15 cm long was prepared from 99.999 pct pure materials and cast in argon. The ingot was placed in an alumina crucible and was direc-tionally solidified at 7 x 10"4 cm per sec in a Bridg-man apparatus in argon. Metallographic examination at both ends and along the length of the ingot showed a uniform structure that consisted of fine alternate plates of silver- and copper-rich phases. The plates were aligned parallel to the growth direction, as shown in the longitudinal section, Fig. 1, and were in small randomly oriented domains of parallel plates as viewed in a transverse section, Fig. 2. Four smaller ingots 0.175 in. in diam were solidified at speeds of 2Xlo-&apos;, 4.4 xlo-&apos;, 4.4 x 10-3, and4.4x10-4 cm per sec to produce a range of lamellar spacings. Replica electron micrographs were taken to resolve the individual plates as shown in Fig. 3. The copper-and silver-rich plates in the larger ingot were about

Jan 1, 1970

By J. B. Cohen, M. B. Beaver, R. J. Black

RECENT investigations have shown that face-centered cubic metals may deform by twinning. Blewitt, et al&apos; found that at 4.2"K the mode of def~rmation of single crystals of copper changed at large strains and markings formed on (111) planes. Later they- emonstrated by X-ray diffraction and metallography that the markings were twins and showed that favorably oriented single crystals of copper deformed by twinning at 78°K. They also observed twinning in silver and gold deformed at 4.2 and 78°K. Wagner3 obtained evidence for twinning from the peak shape of diffraction lines of silver cold-worked at 78°K, but twins small enough to cause such effects are not likely to be detected metal-lographically. In the work reported here lamellar structures were observed in deformed silver-gold alloys. They appeared to be mechanical twins, but metallography could not establish this conclusively. Their tendency to form depended on strain rate, temperature and composition. Specimens of silver-gold alloys (0 to 83 wt pct Au) were deformed plastically. One set was worked by hammering under liquid nitrogen, at room temperature and at intermediate temperatures. Another set was compressed slowly in liquid nitrogen to the same reductions as those produced by hammering. Tensile specimens (0.015 x 0.120 x 1.5 in.) of various compositions and approximately equal grain size (0.011 to 0.016 cm) were tested at -195°C and at room temperature. In microsections of all specimens deformed by hammering at —195°C thin lamellae appeared, Fig. 1. They were aligned in definite directions in each grain. In some grains they had two orientations. Where lamellae intersected, a displacement was apparent. Near the center of the left margin of Fig. 1 shear has taken place beyond the fully developed intersecting lamella. Many lamellae resembled Neumann bands in alpha iron. They were parallel to one side of triangular etch pits in the matrix (as in Figs. 1 and 2). The individual lamellae were narrow and had little substructure. This suggested that they did not result from concentrated local slip. The shape of etch pits within the lamellae differed from that of pits in the matrix, as can be seen in Fig. 2; this indicated a difference in orientation. Specimens slowly deformed at —195°C contained regions in which the lamellae were clustered. In these specimens some lamellae were bent and presumably had formed before the termination of the deformation. Structures of greater width than the lamellae were also seen.4 More lamellar structures formed on impact than during slow compression to a given reduction. This was true of all compositions. The structures became less abundant with increasing temperature of deformation. None was observed after extension to fracture at room temperature, but they could be pro-

Jan 1, 1959

By D. M. Blacknall, N. N. Winogradoff, E. W. Williams

Low-temperature measurements of photolumines-cence were used to evaluate the progvess in materials development. Variation of the impurity type, impurity concentration, and method of growth were used to clarify the chemical origin of defects in GaAs. Melt-g~ozun, epitaxial vapor-, and solution-grown samples were studied. A comparison of measurements at 77" and 20°K shows that more defects can be observed at the lower temperature. Th&apos;vee residual defects were identified in relatively pure GaAs. These were: silicon, copper, and a gallium vacancy-donor complex. Solution growth from a gallium solution inhibits the formation of the latter two. Eleven defects were studied and the "optical" activation energy of some of these, namely, silicon, cobalt, and chromium, has not been reported in the literature before. THE discovery of the injection laser in 1962 prompted extensive measurements of the photoluminescence of GaAs. The measurements were made at 77°K on GaAs doped with shallow impurities at various doping levels and compared with electroluminescence1&apos;2 and absorp- tion data.374 In addition, lower-temperature studies were made on relatively pure GaAS&apos; and on GaAs doped with oxygen,5&apos;" manganese,&apos; and copper.&apos; The observation of defects* in GaAs with photolu- *The word "defects" ~efers to both chemical impurities and native defects. minescence at low temperatures makes photolu mines-cence an invaluable tool in evaluating the progress in materials development. The only previous evaluation was done at 77°K when solution-grown and melt-grown GaAs were compared.O No identification of defects was made but it was shown that some of the deep-level luminescence seen in melt-grown GaAs was absent in solution-grown GaAs. The present work extends the comparison of preparation techniques to lower temperatures and to a study of epitaxial vapor-grown GaAs. It is particularly valuable for thin epitaxial layers since they cannot be analyzed by conventional analytical techniques. In addition, by varying the impurity type and impurity concentration the chemical origin and nature of defects in GaAs was demonstrated. Eleven defects were studied in all. Three of the defects were identified as residual defects which often contaminate GaAs prepared from the melt and the vapor. Only one such defect was observed in GaAs grown from a gallium solution and this was identified as silicon.

Jan 1, 1968

By Lewis W. MacNaughton, F. L. Burchard

The North Texas district, as herein defined, includes the counties of Archer, Baylor, Clay, Coolie, Foard, Hardeman, Knox, Montague, Wichita, and Wilbarger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, are usually modified by stratigraphic changes in the sediments. Excepting the fields in southeastern Baylor, southern Archer, and southwestern Clay Counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsylvanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. DevELopments during 1941 Nearly 1600 wells were drilled in the district during 1941 as compared with more than 1700 in 1940. However, the ratio of successful drilling operations was higher and some 1200 oil wells were completed. Production held about even with the previous year, as did the number of producing oil wells. Known oil reserves increased slightly throughout exploration, which generally was carried on at greater depths than in former years. The average depth of discovery wells was 300 ft. deeper than in 1940. Although discoveries were evenly divided numerically between horizons above the base of the Strawn series and those below the Strawn, the deeper horizons, including the Bend series of the Pennsylvanian, the Mississippian limestone, and the Simpson and Ellenburger of the Ordovician, furnished most of the increase in oil reserves. The largest single addition to the reserves was in the Ellenburger formation in the K.M.A. field. During the year 112 wells were completed in this horizon, bringing the total developed acreage to some 4600 acres. The Straan series in K.M.A. also received considerable development in 1941, with 114 completions. K.M.A. Pressure Maintenance Satisfactory progress was made by the K.M.A. Pressure Maintenance Association in 1941. At the end of the year, 99 wells were being used for input and total monthly volume of gas returned to the reservoir reached a high of 340,548 M cu. ft. in December from a low of 208,853 M cu. ft. in February. Total volume of gas returned during 1941 was 3,306,052 M cu. ft. To the end of the year, 150 cu. ft. of gas had been returned for every barrel of oil produced from the reservoir while the input ratio for December was 397 cu. ft. Per

Jan 1, 1942