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By K. S. Seljesater

Since the development of dispersion-hardenable lead-antimony alloys' in the laboratories of the Western Electric Co., Inc., studies have been made of the effect of various third constituents on these alloys.2 This paper covers a study of the effect of small amounts of arsenic. This element is important since it occurs as an impurity in many commercial antimonial leads and the results obtained are particularly interesting as indicating a class of addition agents which exert a stabilizing effect on dispersion-hardened alloys. Experimental In order to study the effect of increasing amounts of arsenic, a series of alloys were made up containing 1 per cent. antimony, and arsenic varying from 0. to 0.10 per cent., the balance Doe Run lead (99.997 per cent. lead). The alloys were cast into bars 1 1/2 in. wide by 3/4 in. thick and cold-rolled to about 1/8 in- thickness. Three samples of each composition were annealed 1 hr. at 225" C. and quenched in water. One set was aged at room temperature, one at 50" C., and the third at 100" C., the

Jan 1, 1929

By T. M. Allen, W. H. White

THE Greenwood-Grand Forks area of southern central British Columbia, known as the Boundary District, has a long history of mining exploration and production. At the turn of the century this was the premier copper mining camp in the British Empire, its total production amounting to some 20 mil- lion tons. Most of this ore came from the great Granby mines at Phoenix, but the Motherlode mine at Deadwood camp, 6 miles to the west, and several mines in Summit camp, 5 miles north of Phoenix, made important contributions. The large deposits were exhausted in 1918 and the district since has seen only desultory exploration and salvage operations. The orebodies are mineralized skarn zones in limestone members of a thick series of Upper Paleozoic sedimentary and volcanic strata. Chalcopyrite is the primary ore-mineral. Copper carbonates and silicates occur sparingly in outcrops, but the oxidized zone generally is very shallow. Much of the surface is mantled by glacial drift which in most places ranges in thickness from 2 to 15 ft. In some of the hanging valleys, however, the glacial drift may be as much as 100 ft thick and may assume drumlin-like forms.

Jan 1, 1954

By Kenyon E. Richard, James H. Courtright

SILVER Bell is situated 35 airline miles northwest of Tucson, Ariz., in a small, rugged range rising above the extensive alluvial plains of this desert region. Its geographical relation to other porphyry copper deposits of the Southwest is shown on the inset map in the lower left corner of Fig. 1. The climate is semi-arid. Altitudes range within 2000 and 4000 ft. Opening of the Boot mine, later known as the Mammoth, in 1865 was the first event of note in the district's history. Oxidized copper ores containing minor silver-lead values were mined from replacement deposits in garnetized limestone and treated in local smelters. Copper production had approached 45 million pounds by 1909 when the disseminated copper possibilities in igneous rocks were recognized. Extensive churn drill exploration carried out during the next three years resulted in partial de- lineation of two copper sulphide deposits, the Oxide and El Tiro. Although the then submarginal tenor discouraged exploitation of these disseminated deposits, selective mining of orebodies in the sedimentary rocks continued intermittently until 1930, providing a production total of about 100 million pounds of copper.

Jan 11, 1954

By H. C. Boynton, Albert Sauveur

In the course of some experiments conducted in the Metallographical Laboratory of Harvard University, some interesting facts were brought to light which appear to be worth recording in advance of a more elaborate and exhaustive paper which the authors hope to present to the Institute in the near future. Fig. 1 shows, under a magnification of 100 diameters, the microstructure of the cross-section of a steel bar 1/2-inch square, containing 0.52 per cent. carbon, heated to 1100 degrees C. and cooled slowly with the furnace. Fig. 2 illustrates the structure of the same steel, heated to the same temperature but cooled more rapidly in the air. Both samples were cut from the same bar and heated side by side in the furnace. When a temperature of 1100 degrees C. had been reached, one sample was taken out of the furnace and allowed to cool in the air, while the other was cooled with the furnace. The only difference, therefore, in the treatment of both samples will be found in their respective rate of cooling. This variation in the rate of cooling resulted, as shown

Jan 1, 1904

By R. G. Davies, P. Beardmore, T. L. Johnston

The flow stress of a series of Ni-Cr-A1 alloys consisting of a dispersion of y' (based on Ni3Al) in a rnatrix of nickel-base solid solution y has been measured at temperatures up to 950°C as a fwzction of the volume fraction of y'. At high temperatures the flow stress is controlled by the amount of Y' in the alloy, i.e., the higher the volume fraction of y', the greater is the flow stress. This simple relationship is not obeyed at low temperatures in so far as a peak in the flow stress-volume fraction relation occurs at about 25 pct y'. The variation in the mechanical properlies of these alloys as a function of both temperature and volume fraction of y' has been correlated with changes in distribution of both the dislocations and y'. The results are interpreted on the basis that at low temperatures the y matrix is strengthened significantly bv the presence of a hyperfine y' precipitate due to decomposition on cooling; at high temperatures the y matrix is a single phase of low strength. It is clearly recognized that the high temperature strength of most nickel-base superalloys depends upon a dispersion of the ordered fcc phase y', based on Ni3A1, in a fcc solid solution matrix y based on nickel. Although the volume fraction of y' varies widely from about 0.2 in Nimonic 80A to about 0.6 in Mar-M200, all such nickel-base alloys manifest an unusual insensi-tivity of the flow stress with respect to temperature. In Mar-M200 for example, the 0.2 pct flow stress remains essentially constant from room temperature to 750°C. The conclusion has been drawn1 that the characteristically low temperature dependence of the flow stress of y-y' nickel-base alloys is obtained when the state of dispersion of y' is such that dislocations are forced to cut through the y' particles at the onset of yielding. When the spacing between the y' particles is so large that the flow stress is controlled by dislocation bowing between particles, then the initial flow stress decreases progressively with an increase in temperature at a rate determined by changes in elastic properties. The same conclusion is inherent in the detailed, mechanistic model of the deformation process in commercial superalloys which has been developed by Copley and ear' in which the temperature independent flow stress is attributed primarily to the contribution of the antiphase boundary energy created in the y' particles during deformation. In this theory the temperature insensitivity of the flow stress is a reflection of the constant antiphase boundary energy as a function of temperature. An important microstructural parameter that is relevant to the explanations that have been suggested' to account for the temperature insensitivity of the flow stress is the volume fraction of y'. To vary the latter to any significant extent in a given commercial alloy is clearly difficult. However, it is possible in a relatively simple Ni-Al-Cr ternary system which manifests analogous microstructures in terms of the distribution of y' in y and contains specific alloys which have flow properties that depend on temperature in a manner quite similar to their more complex commercial counterparts. Hornbogen et . have studied precipitation phenomena and deformation mechanisms in such alloys but only where the y' volume fraction was small (less than 0.2) and the y' particle size varied from less than 100A up to a maximum of -1000A. In the present study, a series of alloys was prepared in which the volume percent of y' at 900°C was varied from 0 to 100 pct with the y' particle size (of the order 0.5 p) comparable to the sizes obtained in commercial superalloys. Particular attention has been given to the relationship between variations in the volume fraction and distribution of y' and the temperature dependence of the flow stress EXPERIMENTAL TECHNIQUES The Ni-Cr-Al system was selected because it is well characterized, bears a close relationship to commercial alloys, and offers the advantage of an extra degree of freedom over a binary system. In the present investigation, a series of alloys across the tie line between NisA1 and Ni3Cr (Ni3Cr is not an in-termetallic compound, the nomenclature is only used to designate the composition) were vacuum cast. The pseudobinary6 and the composition of the alloys used are shown in Fig. 1. It is important to note that the compositions of the y phase and the y' phase in the two-phase alloys was always the same. Alloy compositions were selected from the binary diagram, Fig. 1, in order that aging at 900°C would produce from 0 (100 pct y) to 100 pct y' by volume percent. (The size of the y' particles produced during the equilibrium aging treatment increased as the volume fraction of y' increased, ranging from about 0.2 p at low volume fractions up to about 0.8 p at the highest volume fraction.) The y' phase is based on the inter-metallic compound Ni,A1 which has the fcc LIZ type superlattice structure, and chromium substitutes for aluminum in the structure. The y phase is a disordered fcc solid solution. The alloys were heat treated at 1150°C for 2 hr, air cooled to room temperature, and finally annealed for 16 hr at 900°C. The rods were then centerless ground to 0.25 in. diam and cut into compression samples 0.5 in. long. The compression tests were made on an In-stron machine at a strain rate of 7 x 10"4 sec-'. A rapid heating radiant heat furnace was used which minimized the heating and temperature stabilization time to 10 min for the highest testing temperature. All the tests were stopped after 5 pct plastic strain.

Jan 1, 1970

By R. G. Aspden

Crystals with an (001) [loo] initial orientation of an iron-base alloy containing 3 pct Si were cold rolled with and without the use of constraints. A major difference in the rolling and annealing textures was observed between crystals rolled with and without constraints. These data show that the contribution of constraints at grain boundaries in a poly crystalline sheet should be considered in applying textural data on single crystals to grains in an aggregate. SILICON-iron alloys with a cube texture have been recently developed and their magnetic characteristics reported.1-4 Of interest in the development of this texture were the textural changes of single crystals accompanying rolling and annealing and the influence of constraints at grain boundaries in an aggregate on the behavior of individual grains. The present study was primarily concerned with the effect of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001)[100]. Barrett and Levenson5 were among the first to observe an influence of constraints at grain boundaries on the textural changes of individual grains during deformation. They tested Taylor's6 theory of plastic deformation of face-centered-cubic metals in which deformation textures were predicted. About one-third of the grains in poly crystalline aluminum did not rotate as predicted. Grains of the same initial orientation were observed to rotate in different directions under the influence of applied stress and anisotropic flow of neighboring grains. Recently, the various inhomogeneities of flow of crystals in an aggregate have been studied7'8 and reviewed.9-11 Barrett and Levenson" rolled (001) [loo] iron single crystals inserted in close-fitting holes in copper to limit lateral flow and to simulate rolling of grains in an aggregate. Deformation bands were formed after a 90 pct reduction in thickness, and the cold-rolling texture contained two components described by rotating the (001)[100] about 35 deg in both directions around the normal of the rolling plane. No annealing textures were reported. Chen and Maddin13 rolled molybdenum single crystals initially (001) [loo]. The crystals were mounted between two hardened silicon-iron plates and 96 pct reduced in thickness by rolling at a low rate of reduction, about 0.0001 in. per pass. The deformation texture had the mean orientation of (001) [loo], and the azimuthal spread included orientations described by rotating (001) [loo] about 35 deg in both directions about the pole of the rolling plane. The presence of deformation bands were not reported by Chen and Maddin or detected in subsequent work of Ujiiye and Maddin.14 The ideal orientation of the annealing texture was (001) [loo]. Recently, Walter and Hibbard 15 reported on the textures of 3 pct Si-Fe alloy crystals initially near (001) [loo]. Each crystal was in an aggregate cut from a columnar ingot. After 66 pct reduction by rolling, the texture consisted of two symmetrical components which had the orientations described by rotating (001) [loo] about 30 deg in both directions about the pole of the rolling plane. Annealing texture was near (001) [loo]. In the above work, the textures of body-centered-cubic crystals were studied after rolling under the influence of constraints. The deformation textures varied from (001) [loo] to near the (001) [110] type and appeared sensitive to the manner in which the crystals were rolled. No textural data were available on the effect of rolling (001) [loo] crystals with and without constraints. The purpose of the present work was to evaluate the influence of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001) [loo]. Rolling and annealing textures were studied for a) crystals rolled with no constraints at different rates of reduction, and b) crystals rolled with constraints imposed by neighboring grains and by plates between which a crystal was "sandwiched". PROCEDURES AND EXPERIMENTAL TECHNIQUES Data are presented on four crystals which are representative of several crystals studied. The orientation of each crystal prior to rolling was (001) [loo] as determined by the Laue X-ray back-reflection method," i.e., each crystal had an (001) within 3 deg of the rolling plane and [100] within 3 deg of the rolling direction. These crystals were obtained from two iron-base alloys containing 3 pct Si by weight which were prepared by vacuum melting electrolytic iron and a commercial grade of silicon. Crystals 1, 2, and S-1 were cut from a large single crystal grown from the melt of one alloy by the Bridgman technique17 in an apparatus described by

Jan 1, 1960

By Peter R. Morris

The effecl of preferred orienlation on X-vay dzffvaction measurements of retained austenzte was investigated for four precipitation-hardening staznless steels in sheet form. A method is preserzted for estimating the ervor in measurement associated with a given samplirig direction. The method was used to select an "optimum" sampling direclion in order to minimize errors in measurement due to preferred orientation. hleasuremenls of retained austenite content employing lhe proposed sampling direction are conzpaved to measuretnents enzploying the more commonly used normal direclion for a series of sawzples. THE first application of X-ray diffraction to the measurement of retained austenite in steels is due to Sekito, 1 who employed a photographic technique in which the (111) reflection from a thin strip of gold affixed to a cylindrical sample was employed as a standard. Averbach 2 introduced the "direct comparison" method in which the ratios of observed to calculated random intensity are assumed proportional to the austenite and/or martensite contents. Averbach's work forms the basis of most subsequent X-ray diffraction methods for the determination of retained austenite. Subsequent improvements are due to: Averbach and Cohen,3 who employed a sodium chloride crystal to monochromate cobalt radiation; Averbach et a1.,4 who introduced a bent sodium chloride monochromator; Mager,' who used a bent quartz crystal to monochromate chromium radiation ; Littmam, who first used a geiger counter diffractometer for this purpose; Beu and Beu and Koistinen, 11,12 who studied effects of absorption factor, surface preparation, sample geometry, integrated intensity vs peak height, choice of radiation, monochromator, and filter. The possibility of errors in measured values due to orientation effects was noted by Miller,13 who suggested examination of a surface other than the plane of rolling. Lopata and Kula 14 have developed an experimental technique in which the preferred orientation is measured in each sample. They illustrated the method for a sample containing 42 pct retained austenite. Application of their technique to the 1 to 15 pct range typical for the precipitation-hardening stainless steels does not appear feasible. EXPERIMENTAL PROCEDURE The nominal compositions of the precipitation-hardening stainless steels investigated are listed in Table I. Ingots were solution-treated, hot-rolled to approximately 0.2 in., and reduced to 0.050 in. by a suc- cession of cold rolling and annealing operations. After this treatment the 17-4PH sample was in the marten-sitic condition, while the 17-7PH, PH 14-8Mo, and PH 15-7Mo samples were in the austenitic condition. Samples of 17-7PH and PH 15-7Mo steels in the mar-tensitic condition were obtained by heating to 1750'F for 10 min and holding at -100°F for 8 hr. A sample of PH 14-8Mo steel in the martensitic condition was obtained by heating to 1700°F for 1 hr and holding at -100°F for 8 hr, followed by aging at 950" for 1 hr. POLE FIGURE DETERMINATIONS Samples were thinned to 0.003 to 0.005 in. by etching in a solution containing 250 ml reagent-grade phosphoric acid (85 to 87 pct H3PO4), 250 ml technical-grade hydrogen peroxide (30 to 35 pct H 2 O 2), and 50 to 100 ml reagent-grade hydrochloric acid (37 to 38 pct HCl). The specimens were placed in an "integrating" sample holder which provided a 1-in. oscillation in the plane of the sample. The diffractometer was aligned to measure the intensity diffracted by planes of the particular {hkl} type being studied. The sample was Set for a given latitude angle, a, measured from the plane of the sheet, and diffracted intensity recorded as the longitude angle, 0, measured in the plane of the sheet from the rolling direction, was increased from 0 to 360 deg. After a 360-deg scan of B, a was incremented by 5 deg, and the process repeated. Random standards obtained by spraying suspensions of powdered iron (bcc structure) and nickel (fcc structure) in lacquer were used to correct observed intensities for absorption and geometrical effects. Zirconium-filtered molybdenum radiation was used to determine the transmission regions of the (111) (0to 45 deg), (200) (0 to 60 deg), and (220) (0 to 45 deg) austenite and (110) (0 to 45 deg), (200) (0 to 50 deg), and (211) (0 to 35 deg) martensite pole figures. Vanadium-filtered chromium radiation was used to

Jan 1, 1968

By M. Schwartz, S. K. Nash, R. Zeman

Knoop hardness in the rolling plane and in the longitudinal plane of hot-rolled and cold-rolled sheets of sublimed magnesiu?w was measured as a function of the angle between the long axis of the indenter and the rolling direction. These measurements were correlated with similar data taken on the (0001) and (1010) planes of a single crystal of magnesium where the hardness was measured as a function of the angle between the long axis of the indenter and the [1120] direction. The results were analyzed for compliance with the hypothesis of Daniels and Dunm to account for slip, and with a similar hypothesis to account for twinning. Some hardness anisotropy data are also presented for magnesium-indium and magnesium-lithium solid solution alloys. It is well known that the hardness of a crystalline specimen is different for its different surfaces, and also that the hardness is a function of direction within a single surface. Variations in hardness for single crystals have been found to be much larger than those for polycrystalline materials. Also, materials having low crystal symmetry were found to have a greater anisotropy of hardness than those of high symmetry. 0'Neill1 and Pfeil,2 using a 1-mm Brine11 ball, studied single crystals of aluminum and iron, respectively; and they found a variation of hardness of about 10 pct between readings taken along the principal crystallographic faces. Daniels and Dunn3 found that the Knoop hardness number varied about 25 pct as the long axis of the indenter rotated on the basal plane of a zinc single crystal. The variation on the (1450) plane was about 100 pct, and the average hardness on this plane was about twice that of the basal plane. They also studied the variation of hardness within the (loo), (110), and (111) faces of a single crystal of silicon ferrite and found variations of about 25 pct although the average values for these planes were almost identical. Single crystals of zinc were also studied by Meincke.4 He found that the Vickers hardness numbers varied about 30 pct depending on whether the axis of the indenter was parallel or perpendicular to the (1010) and (1110) planes. Mott and Ford,5 using a Knoop indenter, found a 25 pct variation in hardness on the basal plane of zinc. Crow and Hinsley6 studied heavily cold-rolled bronze, steel, brass, copper, and other metals. They found that the difference in hardness numbers based on the difference in the length of the diagonals of the Vickers indenter was from 5 to 12 pct. Some minerals and synthetic stones show a very large anisotropy of hardness. Robertson and Van Meter7 found the Vickers hardness of arsenopyrite to vary from 633 to 1148 kg per mm2. stern8 using the double-cone method on synthetic corundum found the hardness number to vary from 950 to 2070. And winchell9 reported a variation of hardness number from 184 to 1205 in kyanite. The variation of hardness as a function of direction in a given crystallographic plane in single crystals possesses a periodicity which is related to the symmetry of the lattice. Daniels and Dunn3 found a six-fold periodicity of hardness in the (0001) plane of zinc. They found that the hardness curves of silicon ferrite had a four-fold symmetry in the (100) plane, a two-fold symmetry in the (110) plane, and a six-fold symmetry in the (111) plane. Mott and Ford5 also reported a six-fold symmetry of hardness in the basal plane of zinc. And vacher10 found two-, four-, and six-fold periodicities of hardness in copper on the (110), (100), and (111) planes, respectively. The purpose of this paper is to report the results of an investigation on the anisotropy of hardness as a function of orientation in single crystals of mannes-ium, and samples of rolled magnesium, magnesium-indium, and magnesium-lithium solid solution alloys. The anisotropy of hardness of pure magnesium which had been hot rolled, and then cold rolled various amounts to fracture, was studied by means of Knoop indentation hardness numbers; and the results were correlated with the preferred orientation as determined by quantitative X-ray pole-figure data. A comparison was made of the hardness data obtained from the rolled sheets and those of single crystals of magnesium. In order to obtain a more fundamental understanding of the variation of hardness and of Knoop hardness testing, the data were analyzed by

Jan 1, 1962

By W. B. Gogarty, W. C. Tosch

A new recovery process for producing oil under both secondary and tertiary conditions utilizes the unique properties of micellar solutions (also known as microemulsions, swollen micelles, and soluble oils). These solutions, which displace 100 percent of the oil in the reservoir contacted, can be driven through the reservoir with water and are stable in the presence of reservoir water and rock. Basic components of micellar solutions are surfactant, hydrocarbon and water. They may also contain small amounts of electrolytes and co surfactants such as a1cohol.r. The specific reservoir application dictates the type and concentration of each component. A salient feature of [he process is the capability for mobility control. Micellar solution slug mobility, by way of viscosity control, is made equal to or less than the combined oil and water mobility. Mobility control continues with a mobility buffer that prevents drive water from contacting the micellar solution. Laboratory and field flooding have proven that the process is technically feasible and that surfactant losses by adsorption on porous media are small. Introduction projects are under way to recover the maximum amount of oil under the most favorable economic conditions.' : New techniques are being developed to increase oil recovery,3" Polymer solutions are becoming an important means of controlling mobility in a waterflood. Thermal methods such as in-situ combustion and steam injection are being used in reservoirs containing highly viscous crudes. Surfactant flooding is receiving attention as a method of reducing interfacial tension to increase recovery.*'" Exotic recovery processes have been considered primarily for ' perations. Economics are unfavorable in most cases for tertiary recovery. studies at the Denver Research Center of the Marathon oil CO. have led to a new oil recovery method.* Micellar solutions (sometimes called microemulsions, swollen micelles, and soluble oils) are used to recover oil by miscible-type waterflooding. Basically, these solutions contain surfactant, hydrocarbon, and water. The method can be used in either secondary or tertiary operations. First, thc concept of thc process is considered in terms of the requirements for an effective miscible waterflood ing operation. Next, micellar solution properties are described including structure, composition, and phase behavior with reservoir fluids. Fluid characteristics are then considered as related to mobility control, and, finally, laboratory and field results are presented to illustrate the efficiency of the process. Concept of the Process Unit displacement efficiency and conformance determine the effectiveness of any oil recovery mechanism. In theory, a miscible waterflood should be capable of a 100-percent unit displacement efficiency with a correspondingly high conformance. Requirements for the slug of a miscible waterflood include (1) 100-percent displacement of oil in the reservoir contacted, (2) controllable mobility, (3) the capability of being driven through the reservoir with water, (4) a low unit cost to enhance economics, and (5) the ability to remain stable in the presence of reservoir water and rock. Micellar solutions satisfy requirements for the slug of a miscible waterflood process. Our discovery that these solutions acted as though they were miscible by displacing all fluids in the reservoir and by being displaced by water solved the miscibility problem. Adequate mobility control is possible by variations in solution viscosity through compositional changes. Economic requirements are met since micellar solution costs below $6/bbl appear possible, Mi cellar solutions stabilize surfactant in the presence of reservoir rock and water, thus reducing the importance of the problem of surfactant loss by adsorption. Fig. 1 illustrates schematically how these solutions are used. Operations start with injection of a micellar solution slug that serves as the oil displacing agent. Next, a mobility buffer of either a water-external emulsion or water solution containing polymer (thickened water) is injected to protect the slug from water invasion. Finally, drive water (water used in a regular waterflood) is injected to propel the slug and mobility buffer through the reservoir. Reservoir oil and water are displaced ahead of the slug, and a stabilized oil and water bank develops as shown in Fig. 1. Stabilized bank saturations are independent of original oil and water saturations. This means that, for a particular type of reservoir, the displacement mechanism is the same under secondary and tertiary recovery conditions. Oil is produced first in a secondary operation. For tertiary conditions, water is produced first. Movement of the slug through the reservoir is stabilized by the mobility buffer. An unfavorable mobility ratio usually exists at the interface between the buffer and drive

Jan 1, 1969

By Larry Kaufman, Martin Schatz

The effect of pressure on the extension of the ? loop in the FeSi system has been determined by means of metallogvaphic studies and hardness measurements performed on a series of high-purity Fe-Si alloys containing 7.5, 11.0, and 13.9 at. pct Si, respectively. These mensurements, performed at 42 kbar and temperatures up to 1200oC, indicate that the ? loop is expanded to about 10 at. pct Si at 42 kbar as opposed to a maximum extension of 4 at. pct Si at 1 atm. Comparison of the experimental results with thermodynamic predictions of the pressure shifts yields satisfnctory results. DURING the past few years, several studies have been performed in our laboratory1-' in order to determine the effect of high pressure on phase equilibrium in pure iron and iron-base alloys. The purpose of these studies has been to elucidate the effects of high pressure experimentally and to compare the observed results with predicted pressure effects derived on the basis of known thermody-namic and volumetric data at 1 atm. These studies have included work on pure iron2,5,7 as well as Fe-Ni,1,5 Fe-cr,l,5 and Fe-c4-6 alloys. In addition, Tanner and Kulin3 have reported results of pressure studies on two Fe-Si alloys containing 2.0 and 6.25 at. pct Si. At the time of this latter study, no detailed information was available concerning the difference in volume between the a (bcc) and ? (fcc) phases in the Fe-Si system as a function of silicon content. In order to compare their observations with calculated pressure shifts, Tanner and Kulin were forced to assume that silicon had no effect on the difference in volume between a and ? iron. The resulting discrepancy between their calculation of the a/? phase boundary at 42 kbar and the observed results led them to the conclusion that silicon additions probably decrease the difference in volume between a and ? iron. Recently: Cockett and Davis8,9 have reported de- tailed studies of the lattice parameters of a series of Fe-Si alloys at temperatures ranging from 20" to 1150°C. These measurements, performed on alloys in the bcc and fcc range, show that silicon does indeed decrease the difference in volume between a and ? iron. By correcting the calculations of Tanner and Kulin in line with the observed effect of silicon they were able to show improved agreement between computed and observed pressure shifts.' The present measurements were undertaken to provide additional corroboration of this effect, by extending the range of composition, in addition to exploring a situation where large extensions of a ? loop could result in impingement of the ? field with an ordered bcc phase (based on Feo.75Sio.25). I) EXPERIMENTAL PROCEDURES AND RESULTS The alloys investigated were obtained from Dr. F. Kayser of M.I.T. They were prepared at the Ford Scientific Laboratory by vacuum melting electrolytic iron and high-purity silicon. The melts were poured under an argon atmosphere into hot-topped steel molds. Subsequently the ingots were hot-worked down to 1/2-in.-diam rods. Three alloys containing 7.5, 11.0, and 13.9 pct Si were studied. Carbon, regarded as the principal impurity, analyzed at, or below, 0.001 wt pct for all of the alloys. Prior to pressure-temperature treatment, the rod was annealed for 24 hr in vacuum at 1000°C, water-quenched, and subsequently machined into 0.100-in.-diam by 0.100-in.-long specimens. Subsequent to machining, the specimens were again annealed and then examined metallographically. They were found to exhibit a clear coarse-grained ferrite similar to Figs. 10 and 110 of Ref. 1 and Fig. 2 of Ref. 3. Subsequently, specimens of each alloy were equilibrated at 42 kbar at various temperatures in supported piston apparatus.1,3,4,6 Three specimens, one of each alloy, were wrapped in platinum and exposed simultaneously. The pressure-temperature cycle consisted of increasing the pressure from ambient to 42 kbar at 25oC, heating rapidly to the desired temperature, holding for 15 min, and quenching to 100°C, followed by slower cooling to 25°C and pressure release. The temperature was measured with a Pt/Pt-13 pct Rh thermocouple which was not corrected for pressure effects. Subsequently, specimens were examined metallographically and by

Jan 1, 1964

By Emmanuel P. Papadakis

Ultrasonic velocity measurements have been made to study the preferred orientation in cube-textured copper. Methods applicable to thin specimens were employed since the specimens were necessarily of sheet material. The measured velocities in various directions in the sheet differed from the corresponding values in single-crystal copper by 1 to 6 pet. The distribution of the deviations indicated that the align-ment of the (001) planes with the rolling plane was better than the alignment of the [100]and [010] directions with the rolling and transverse directions. Ultrasonic pole figures (velocity us orientation) are shown to be useful in the study of preferred orientation. THIS paper describes one set of experiments in a continuing study of preferred orientation in worked metals. This study has been undertaken to investigate the fundamental properties of metals when used as propagation media for ultrasonic waves. Many such materials are of current or potential use in ultrasonic delay lines. Fundamental studies on ultrasonic propagation parameters such as velocity, attenuation, and diffraction (beam spreading) are of importance in the design of delay lines, in the development of nondestructive testing methods, and in the study of materials themselves. Preferred orientation in worked poly-crystalline metals influences all three above-mentioned parameters, and hence is of particular importance. When polycrystalline metals are subjected to mechanical working, they develop textures dependent upon their crystal structure and the symmetry of the working operation.' The texture consists in the alignment of the crystallographic axes of the grains in preferred directions with respect to the symmetry axes of the working operation. Since the grains are elastically anisotropic, the elastic moduli of worked metals are anisotropic. Hence the velocities of elastic waves in worked metals depend on the directions of propagation and polarization. The worked metal may be thought of as taking on the elastic symmetry of a single crystal: so it possesses the same number of independent elastic moduli as the crystal class it simulates. In general, a worked metal does not adopt the crystalline symmetry of its own grains. For instance, most rolled sheet becomes effectively orthorhombic while all bar stock and wire develop hexagonal symmetry. However, certain metals with cubic crystal structure develop a cube texture upon rolling and annealing.= Nearly perfect alignment of [100]-type directions with the rolling direction, transverse direction, and rolling-plane norma1 can be achieved in certain fcc metals and alloys. These cube-textured rolled metals provide an excellent opportunity to test preferred orientation by means of elastic waves, since a worked metal with 100 pct cube texture would have elastic moduli identical to the moduli of its constituent metal. It is the purpose of this paper to present the results of an investigation upon cube-textured copper. Ultrasonic waves were used. The methods of measurement and the experimental results on the effective moduli will be given. The ultrasonic measurements will be shown to complement X-ray pole figures for the determination of preferred orientation in worked metals. EXPERIMENT To study cube - textured material, it was necessary to use thin-sheet material since a severe reduction in gage (95 to 99 pct) is necessary to produce cube texture. Special ultrasonic methods were needed to investigate the thin material at megacycle frequencies. A) Materials. The cube-textured material tested was a copper alloy containing 1 pct Zn. Specimens already measured for Young's modulus4 by Alers were kindly supplied by him. The specimens were slabs 3.00 by 0.25 in. cut from sheet 0.047 in. thick. The orientations of the long axes of the specimens with respect to the rolling direction were taken in 15-deg steps from 0 to 90 deg. B) Measurements. Two distinct experiments were performed to measure the phase velocity in these specimens. One measured the shear wave velocity for propagation in the 0.25-in. direction and polarization in the 3.00-in. direction. The other measured the velocity of both shear and longitudinal waves propagating in the thickness direction in the sheet. 1) Plate-Mode Measurements. The velocity of the zeroth-order shear mode5 was measured in the 0.25-in. direction in each strip. The specimens were ground thinner over half their length to assure that the first-order shear mode would be cut off below 6 Mc per sec, leaving the zeroth-order nondispersive shear mode as the only propagating mode. Piezoelectric ceramic transducers of 5 Mc per sec resonant frequency poled in their long direction were solder-bonded to the edges of the thin part of the slabs as in Fig. 1 after these edges had been made flat and parallel by fine grinding. These transducers produced waves polarized in the 3.00-in. direction and propa-

Jan 1, 1967

By A. E. Blakeslee

Morphological and electrical properties of GaAs epitaxial layers are influenced not only by changes in the nominal substrate orientation but also by small amounts of misorientation from the exact crystal planes. Deviations up to 5 deg from {11IA}, {11IB}, and (100) planes were investigated. Growth rates increase progressively with angle, approximately I u per hr per deg. Size and density of growth pyramids fall off with increasing angle, but other effects that are deleterious to the surface may occur which are heightened by increased misorientation. Carrier concentration decreases and electron mobility consequently increases as the angular offset increases, except in the case of strong compensation, where the mobility trend is reversed. It has long been known that changes in the crystallo-graphic orientation of the substrate may cause pronounced effects on the morphological properties of vapor grown semiconductor films. Reports of orienta-tion-dependent growth rates and surface characteristics are as old as the literature on epitaxy itself. shawl has recently published a comprehensive study of the dependence of growth rate on substrate temperature and orientation in epitaxial GaAs. It is also well-known that misorienting the substrate surface a few degrees away from the nominal low-index crystal-lographic plane often produces a much smoother epitaxial surface. This was reported by Tung2 for silicon, Reisman and Berkenblit3 for germanium, and by Kontrimas and Blakeslee4 for GaAs, and use is commonly made of this fact in the semiconductor industry to help guarantee smooth vapor deposits. The effects of substrate orientation on the carrier concentration and mobility of vapor grown GaAs were first documented by williams5 in 1964 and have been observed by several other authors since then,6,7 but no one has yet reported a careful study of how small changes influence these properties. We have made such a study and have found that sizable differences in growth rate, morphology, carrier concentration, and mobility can indeed be observed for epitaxial films grown on substrates that are oriented by progressive small increments away from the exact crystal plane. EXPERIMENTAL Early in the investigation an arsine synthesis system of conventional design8 was employed to produce growths on {111A}-oriented GaAs substrate crystals. In that early work, pronounced effects on carrier concentration and electron mobility were observed as a function of slight misorientation from this low index plane. That observation led to the more careful study that is reported here. An AsC13 system, differing in major aspect from those commonly in use today9 only in that the reactor is vertical rather than horizontal, was used for the detailed study. The gallium source was at 900°C and the substrates were at 750°C. The flow rate of pal-ladium-diffused H2 through the AsCl3 bubbler was 200 cu cm per min, and the flow rate of bypass H2 was also 200 cu cm per min. The substrates consisted of chro-mium-doped semiinsulating GaAs to facilitate elec-trical evaluation of the overgrowth by means of Hall and conductivity measurements on conventional eight-legged Hall bridges. They were misoriented by 0 to 5 deg from the {111A}, {111B}, and (100) planes, toward the (100) from the {111A} and {111B} and randomly toward the <111A> or <111B> from the {loo). The crystals were oriented for sawing by the Laue back-re-flection technique, which is good only to about ±1/2 deg; but after polishing or sometimes after epitaxial growth the wafers were checked by a diffractometer technique which is accurate to about * 0.1 deg. After lapping, the wafers were polished with NaOCl after the technique of Reisman and Rohr,10 and just before use they were cleaned in NaOC1, thoroughly rinsed with de-ionized water, and blown dry with nitrogen. Each run employed four wafers, each misoriented by differing amounts from one of the three major faces, and at least two runs were made for each orientation. The runs were continued long enough to provide at least a 15-µ or thicker layer. SURFACE MORPHOLOGY The appearance of all the films that were grown in a given run always changed from wafer to wafer as a function of increasing misorientation, but not always in the same regular fashion. At least three different trends were observed. These are more easily seen than described, and reference to the series of photo-

Jan 1, 1970

By A. Szirmae, Hsun Hu

The early stages of recrystallization in a 70 pct cold-rolled Si-Fe crystal of the (110) (0011) orientation were studied with a Siemens electron microscope. Orientation studies based on electron-diffractzotz. patterns confirm the results of previous texture analysis. The driving energy for recrystallizatior and the critical radius for growth were calculated from the dislocation energy and the energy of the subgrain bourzdaries, and it was found consistent with the observed size of the recrystallized grains. The recrystallization characteristics of crystals with different initial orientations are discussed. The recrystallization of cold-rolled (110)[001] crystals of Si-Fe has been widely studied by various investigators.1-4 Their results on both deformation and annealing textures are in good agreement. The rolling texture after 70 pct reduction consists mainly of two crystallographically equivalent (111) [112] type textures and a minor component of the (100) [011] type. The latter is derived from the deformation twins, or Neumann bands, which are formed during the early stages of deformation and later rotate to the (100) [011] orientation upon further rolling reduction. Between the two main (111) [112] type textures, there is some orientation spread, because of which very low intensity areas appear in the pole figure. If these very low intensity areas are considered to be a very weak component in the texture, then a (110) [ 001 ] orientation may be assigned to them. When this rolled crystal is annealed at a sufficiently high temperature for recrystallization, the texture returns to a simple (110) [001]. The purpose of the present investigation was primarily to seek a better understanding of the recrystallization process by using the electron transmission technique. The (110) [0011 type of crystal was selected because orientation data for it are well known from previous studies with conventional techniques. Direct observations on the recrystallization of such a crystal have also been made by using a hot-stage inside the electron microscope, and the results will be reported in another paper. MATERIAL AND METHOD A single-crystal strip of the (110) [001] orientation was prepared from a commercial grade 3 pct Si-Fe alloy by the strain-anneal technique.= The strip was approximately 0.014 in. thick, and was rolled 70 pct at room temperature to a thickness of 0.004 in. Specimens were cut from the rolled strip and were annealed in a purified hydrogen or argon atmosphere. They were then electrolytically polished in a chromic-acetic acid solution to very thin foils. Best results were found by polishing first between two narrowly spaced flat cathodes with the specimen edges coated with acid-resisting paint, followed by polishing between two pointed electrodes until a hole appeared in the center as described by Bollmann.6 It was found that a thin transparent film always formed along the thin edges of the polished specimen. This film was then removed by rinsing the specimen very briefly in a solution of alcohol with a few drops of HF or HCl. RESULTS AND DISCUSSION 1) The Deformed Crystal. From the electron-diffraction patterns taken at various areas of an as-rolled specimen, the texture components as deduced - from ordinary pole-figure analysis were confirmed. Over most of the areas where orientation was examined, a (111) pattern with a [112] direction parallel to the rolling direction was obtained. This corresponds to the main deformation texture of the (111) [112] type. In a few areas the diffraction pattern was (100) [Oil], corresponding to the minor-texture component derived from the Neumann bands. The (110) [001] orientation, which corresponds to the very weak intensity area in the pole figure, was found infrequently. A typical example of the deformed matrix having the (111) type main texture is shown in Fig. 1, where (a) is the microstructure and (b) is the diffraction pattern taken from that area. It was also frequently observed that in other areas more or less continuous rings of weaker intensity were superimposed on the simple (111) diffraction pattern, suggesting the presence of a wide range of additional orientations. Other evidence indicated that the recrystallization characteristics are different in these two different types of areas. The hot-stage observations which provide this evidence will be discussed in another paper. AS shown in Fig. l(a), numerous dislocation-free areas of very small size are embedded in the "clouds" of high-dislocation density. This indicates that the deformation of a single crystal, even after a rolling reduction of 70 pct, is far from uniform on a micro-

Jan 1, 1962

By H. T. Green, R. M. Brick

True stress-strain data on alloys of pure iron with up to 2.4 pct Al were obtained in the temperature range +100° to —185°C. Alumi-num was found to reduce yield and flow stresses of iron at low temperatures but to have little or no effect on ductility. The effects of temperature and composition on strain hardening are discussed. SEVERAL independent studies of the behavior of high purity iron binary alloys at low temperatures are now in progress in attempts to evaluate systematically the variables affecting the low temperature brittleness of ferritic steels. This paper reports the results of one such investigation in which the tensile properties of aluminum and aluminum plus silicon ferrites were measured from 100" to —192°C. True stress-natural strain data have been obtained in order to evaluate as many as possible of the parameters which describe the behavior of the materials involved. In comparable studies at the National Physical Laboratory in England, iron and iron alloys of high purity have been produced&apos; and tested at subat-mospheric temperatures.&apos; True stress-natural strain curves were obtained there also. The purest iron contained 0.0025 pct C and 0.001 pct O and N. Even this, as normalized at 950°C following hot rolling, showed little ductility at -196°C. The grain size was ASTM No. 3, and the room-temperature yield strength was 17,800 psi (which seems too high for pure iron). Some of the NPL irons contained considerably more oxygen and demonstrated intergran-ular fracture at —196°C. The authors2 carefully differentiated between intergranular fractures associated with excessive oxygen content and transcrys-talline cleavage with little ductility encountered at —196°C in the purer material. The cleavage stress was half again as great as that associated with inter-granular fracture. Test Material, Preparation, and Procedures Of a number of Fe-A1 alloys produced, eight were considered to be sufficiently pure for testing. Partial chemical analyses (Table I), low observed yield points, and high ductilities indicate these alloys to be comparatively pure for vacuum-melted irons of sizable ingots, 5 Ib or more. To produce the binary Fe-A1 alloys, electrolytic iron was melted in air, cast into slabs, and rolled to strips 0.010 in. thick. These strips, joined into a continuous ribbon and wound into 2 1/2 in. diameter spools, were subjected for four weeks to a moving atmosphere of purified dry hydrogen in a stainless-steel tube at 1050" to 1150°C. Charges of these spools were melted in beryllia crucibles under good vacuums (1 micron), and aluminum (99.97 pct Al) was added to the melts. Compositions of these alloys are recorded in Table I. The ingots were hot forged and then cold rolled at least 65 pct to 3/8 in. rods which were vacuum annealed to the desired grain size, approximately ASTM No. 4, prior to machining into tensile test bars. All tensile specimens had gage sections 1 in. long, with a fillet of 1.5 in. radius to the shoulder. Gage diameters were 0.250 in, except for a few rods where additional cold work required use of a 0.200 in. gage section. After machining, 0.002 in. was removed from the gage diameter using 240, 400, and 600-grit metallo-graphic papers. The final polish with 600 grit left the fine scratches running in the longitudinal direction. By this means, surface metal strained during machining was removed. A few specimens heat treated after machining were similarly reduced 0.004 in. to remove any material affected chemically by the atmosphere during heat treatments, as is discussed in a later section. Tensile tests of the eight alloys at constant temperatures from +100° to —185°C were performed in apparatus which has been described." The essentials include a double-walled insulated metal vessel which contained the liquid heat-transfer medium surrounding the test specimen. A constant temperature was maintained by means of a pyrometer which regulated the pressure of dry air driving liquid air through a copper coil. Temperature variation was less than ±2°C during a specific test. For axial straining, two lengths of case-hardened chain, terminating in simple shackles, loaded the specimen through threaded grips. The lower grip bar passed through a hole in the bottom of the test vessel to which it was joined by a thin-walled

Jan 1, 1955

By Forrest V. Williams

The dislocatiorl and stacking-fault structuve of epitaxial GaAs1-,PX lms been examined by chemical etching. The layers were groun in the (100) direction and etch Pils were developed on (111} planes which nad been lapped and polished on the epiLaxia1 layevs. Tile effecL of the jollolcing cariables on the quality of the epilaxial layers has been examined: doping leuel, grouth rate, and composition. High stacking-faullL densilies weve found in the GuAsi_xpx layers. These are not observed in heavily dolled epitaxial layers tzar in layers with low phosphorus compositions. The dislocatiorz density in GuAsi-x px was highest at the sub-stvate- epilaxia1 layer interface. Composilion changes introduced dislocations in the epitaxial layers. ManY semiconductor p-n junction lasers of Group TIT-Group V compounds and their alloys have been reported in the past several years. Laser action at visible wavelengths in GaAsl-x,Px was first reported by Holonyak and Bevacqua. GaAs, a direct transition semiconductor which lases, and Gap, an indirect transition semiconductor which does not lase, form a continuous series of solid solutions.2 Laser junctions can be fabricated in GaAsl-xPx crystals with phosphorus compositions up to about 40 mol pct. In addition to the production of coherent radiation in these crystals, the efficient recombination radiation of p-n junctions in this material has equally important potential in the development of low-power semiconductor lamps. To achieve a high conversion efficiency of electrical to optical energy in p-n junctions in this material, the relation of physical properties of the crystal to luminescence efficiency must be better understood. Although the electrical, optical, and device properties of GaAsl -xPx junction lasers are understandably of considerable interest, the work to date indicates that the more serious problems are the chemical and metallurgical difficulties encountered in the growth of this material.3 In addition to the problems of chemical purity, crystal imperfections, such as dislocations and stacking faults, can be expected to affect both the efficiency of the radiative recombination process and the perfection of the p-n junction.3 The last requirement, i.c., that of the perfection of the p-n junction, is a particularly troublesome one in the fabrication of laser diodes. To obtain good laser diodes, the p-n junction must be flat, which permits the radiation to be reflected from the resonant cavity boundaries. Junction planarity is extremely sensitive to the crystal perfection of the semiconductor material. Also, it is known that at high dislocation densities (-105 per sq cm) it has not been possible to build laser junctions in GaAsl-xPx . Few studies have been reported on the crystal defect structure of GaAsl-,P,. The first serious study seems to be that of Wolfe, Nuese, and Holonyak,3 who examined the dislocation structure of monocrystalline bulk (nonepitaxial) material grown by halogen vapor transport. In this paper are reported some observations on the dislocation and stacking-fault structure of GaAsl_,P, crystals grown by a vapor transport process on substrates of GaAs. EXPERIMENTAL Crystal Growth. The GaAsl-xPx crystals were grown in an open-tube flow system, using two sets of reagents. GaAs, Pr(red), and HC1 were employed in one method. The transport reaction is =950JC GaAs+HC1 = GaCl +1/4As4 +1/2H2 and the deposition reaction is 2GaAs1-xPx +GaCl3 Composition control is obtained by the flow rate of the HC1 and the vapor pressure of the P4, which is maintained in a separately controlled furnace. The second method has been described by Ruehr-wein4 and utilizes gallium, AsH3, PH3, and HC1. The same transport and deposition reactions as above are involved. Composition control is obtained solely by the flow rates of the three gases involved. All of the crystals were grown on chemically polished GaAs substrates oriented on the (100) plane. The thicknesses of the epitaxial layers were typically 100 to 300p. Revealing of Dislocations. Dislocations were re-vealed on both the( 111 ) and { l l l }b faces by chemical etching. The specimen to be examined was mounted at 54.7 deg, lapped on glass with 3-p alumina, polished on cloth with 3-p diamond paste, and, to remove work damage, chemically polished at room temperature for

Jan 1, 1968

By R. M. Hudson, P. E. Perry

Weight-gain data obtained by nitriding low-carbon sheet steel in an amrnonia CNH,) atmosphere indicated that the process obeyed a parabolic rate law. The calculated actization energy for nitriding in the range 964" to 1268°F agreed reasonably well with published data. At 1358"F, rate data indicated that the activation energy decreased. Weight-gain data obtained by uszng mixtures of NH3 -Nz at 1268°F containzng jrom 10 to 100 zol pct NH3 also obeyed a parabolic rate law. The rate of &apos;nitriding increased with an increase in the NH3 content of the gas Mixture. It is well-known that steel heated in gas mixtures containing ammonia (NH3) takes up much larger quantities of nitrogen than steel heated in nitrogen, both gases having a total pressure of 1 atm;&apos; this phenomenon can presumably be attributed to the catalytic decomposition of NH3 on the steel surface to furnish nascent (monatomic) nitrogen. This process was studied bv Brunauer. Jefferson, Emmett, and Hend-ricks at furnace temperatures of 752" and 831°F2 using mixtures of NH3 in Hz. Englehardt and wagner3 reported that, at a furnace temperature of 914°F and under their experimental conditions, both nitriding and denitriding were controlled by the rate of gas-metal reactions at a steel surface rather than by the rate of diffusion of nitrogen in iron. The present study was undertaken to obtain information on the kinetics of nitriding low-carbon steel strip at higher temperatures so that practical rates for short-time strip-annealing treatments could be estimated. Variables studied included time: temperature, and NH, content in the annealing atmosphere. Mechanical and chemical characteristics of steel nitrided in this manner will not be considered in the present article. MATERIALS AND EXPERIMENTAL WORK The samples used were from a commercial low-carbon steel, 0.0244 cm thick, in the cold-reduced condition. The chemical composition of this steel is given in Table I. Panels were cut to 5.1 by 17.8 cm, degreased in toluene, and weighed just before treatment. Four specimens were nitrided under each of the experimental conditions. A study was made of the nitriding rate of steel in a 100 vol pct ammonia atmosphere, 740 mm pressure, at five specific temperatures within the range 964" to 1358°F. The nitriding rates of steel in ammonia-nitrogen gas mixtures containing 10, 18, 26, 50, and 100 vol pct ammonia, 740 mm total pressure, at 1268°F were also determined. All atmospheres used were dried by successively passing them through drying towers packed with soda lime and with Linde Molecular sieve Type 4A. Quoted gas compositions refer to those entering the furnace. Specimens were held in the constant-temperature zone of a vertical annealing tube furnace for times of 14, 3, 5, 10, or 15 min. Gas flow rates were maintained at 3.8 cu ft per hr, which was nineteen volume changes per hour for the system used. The rate of flow was selected to provide a high level of free NH3 for cracking on the steel surface where the ammonia gas is most effectively used as a nitriding agent. The vertical annealing tube furnace consisted of a Hevi-Duty tube furnace with a 2 1/2-in.-ID mullite ceramic high-temperature tube. The constant-temperature zone (controlled within 10°F) was about 10 in. long. After each specimen was degreased, a hole was punched in one end, for attaching the specimen by hook to a chain so that it could be lowered into or raised from the high-temperature portion of the tube by means of a power-driven winch. A stainless-steel access port with O-ring seals was connected by suitable glass-to-metal seals to the cool upper portion of the furnace tube. After the weighed specimen was placed in the access port, the furnace tube was evacuated to approximately 10"3 torr, and then the system was flushed thoroughly with the atmosphere under study. When the gas flow rate and constant-temperature zone of the furnace were established, the specimen was lowered into the constant-temperature zone. The atmosphere flowed from the top to the bottom of the vertical furnace tube and was then vented. For all these runs, during the first 3 min of the time the specimen was in the constant-temperature zone of the furnace the specimen was heating up to the tempera-

Jan 1, 1970

By T. E. Watkins, M. D. Nelson

INTRODUCTION Deeper drilling for oil is becoming more and more the rule rather than the exception. With deeper drilling come additional problems, perhaps the greatest being those brought on by the higher temperatures encountered down the hole. particularly in the Gulf Coast region of Texas and Louisiana. Temperature gradients of the order of 1.8° to 2.0°F/100 ft are not unusual, and a gradient of 2.3"F.&apos;100 ft is found in some areas of Texas. With a mean surface temperature of 74oF, the following temperatures could be expected for a geothermal gradient of 2.0°F; 100 ft: at 10,000 it. 271°F. 12,000 ft, 314°F: 14,000 ft, 354,oF; and 16.000 ft. 394°F. Severe gelation of lime-base drilling fluid in wells that have high bottom hole temperatures has become perhaps the most serious difficulty enconntered in drilling under such conditions. Lime-base drilling fluids have been very succesefully and widely used in the drilling of wells in the Gulf Coast region because of their inherent stability toward contaminants. their ability to suppress the swelling dispersion of bentonitic shales, and their ease of maintainance. The gradual recognition: during the past few years, that these muds were. in themselve. the cause of many difficulties experienced in drilling has led to wide-pread efforts by the drilling industry. to determine the reasons for the failure of these mud systems and to develop mud systems capable of performing satisfactorily under high-temperature conditios. MANIFESTATIONS OF HIGH-TEMPERATURE GELATION it is generally possible to recognize the symptons of high-temperature gelation early enough that advance predictions can be made of serious difficulties. in mud control, and the useful life of the drilling fluids can be extended by proper treatment. Following i.; a list of the manifestations of high-temperature gelation: (1) The drill string &apos;takes weight&apos; while going in the hole after a trip. In early stages of high-temperature gelation it is possible to notice a slight reduction in drill string weight as the drill pipe is lowred near the bottom of the hole. (2) Excessive pump pressure is required to .tart the circulation of drilling fluid at or near the bottom of the hole when going hack to bottom after a trip. As the severity of the gelation increases it may be necessary to break circulation a number of times when going in the hole. (3) The drilling fluid from the bottom of the hole is thick and often granular or lumpy when pumped up after making a round trip. In a severely gelled drilling fluid system such a condition may be irreversible; that is, it cannot be stirred or chemically treated to produce a satisfactory drilling fluid. (4) Completion tool.. such as logging tools or perforating guns will not sink to the bottom of the hole. On some occasions completion tools will become stuck and require a fishing job to retrieve them if the wire line attached to them is broken. It is often difficult to determine whether the condition of the drilling fluid is responsible for sticking the tool or whether the wire line becomes key seated in a crooked hole and causes the allow difficulty. When there are 110 other symptoms of high-temperature gelation. then the difficulty may usually be attributed to the latter cause. (5) In extreme cases of high-temperature gelation it is necessary to "wash" and "ream" when going back to bottom after coming out of the hole. (6) In many -instance. it has been found to be extremely difficult and expensive to 1111 production packers 2nd tubing in moderately deep oil wells which had been drilled with a lime-base drilling fluid. In such instances-the original mud had apparently "set" to a consistency approaching that of a weak cement. CAUSES OF HIGH-TEMPERATURE GELATION Extensive test; have indicated that a lime-base mud does not develop a highly gelled condition at temperatures below 250°F. whereas above that temperature such condition often develops rapidly. (Fig. 1) concurrently. the following changes are evident ill the mud: (1) The alkalinity of the mud decreases to a very low value. with both caustic soda and lime being consumed. (2) The quartz content of the mud decreases sharply. (3) The bentonitic content of the mud decreases or di-appears, with concurrent decrease or loss of base exchange capacity of mud solids. (4) New compounds formed in the mud have been found to be cal-cium silicate, calcium aluminum silicate, and calcium sodium aluminum silicate. (5) The mud loses the ability to form a filter cake of low permeability. The above characteristics have been discussed, in part. by other authors

Jan 1, 1953

By C. N. Garman

Homestake-New Mexico Partners operate a 750-tpd carbonate leach uranium concentrate mill near Grants, N.M. The highly mineralized water available as process water leaves much to be desired. The 628 ppm as CaCO 3 makes the use of raw water very troublesome in pipes and on filter cloths. However, the residual sodium carbonate in the final filter cake going to tails makes an ideal softening agent. To take advantage of this fact, all makeup water used in the mill is first used as tailing slurry dilution water and comes to the mill from the tailings pond. The 5-acre tailings pond serves as a thickener and 100 to 150 gpm of nearly clear solution is decanted to a pump to be returned to the mill. Since this tailings water has small quantities of uranium in the solution an ion exchange scavenger unit was installed to remove as much uranium as possible. The ion exchange raffinate is then used as final filter wash ahead of the tailings slurrying step. In spite of the large settling area this return water is not clean enough for ion exchange feed. The solids present are very fine and composed of approximately 15 pct (by weight) burnable carbonaceous material common to the sandstone uranium ores in the area, 40 pct SiOz plus 45 pct CaC03. Laboratory work showed that this material responds very well to flotation. Before deciding to use flotation, various clarifying systems such as pressure leaf filters, sand filters, and continuous vacuum pre-coat filters, were considered. Each of these could have solved the problem but with much more operating labor, more reagents and greater installation costs than the flotation step. About 100 to 150 gpm of fouled water is fed to two 66-in. Fagergren cells, in series. Reagents used at the beginning were Arquad 2HT75 and Arquad C50, at the rate of about 1% lb per 8-hr shift, or about 0.0053 lb each per ton of ore. This did not completely remove the solids but does an acceptable job. Approximately 75 pct of the slimes are a size that can be caught on a 41-Whatman Paper are removed. Removal of these slimes also allows much better settling of the coarse nonfloatable material. Advantage is also taken of this fact in a small settling tank ahead of precipitation. Removal of this amount of the slimes makes the ion t:xchange feasible. PREGNANT SOLUTION CIRCUIT The carbonate? leach-caustic precipitation method of uranium concertration does not provide for any process purification step ahead of precipitation. Therefore, any fine solids getting into the pregnant solution through the filter cloth show up in the final concentrate. This, of course, lowers the grade, and, at times, the slimy nature of these very fine solids rendered final filtration of the concentrate difficult if not impossible At Homestake-New Mexico Partners a 75-ft thickener was available for gravity clarification of 100 to 120 gpm of this pregnant solution. However this did not sufficiently remove the slimes. Laboratory investigation of the whole range of flocculants that were suggested by literature, salesmen, and friends failed to turn up anything of consequence. A continuous vacuum pre-coat filter would do the job and was investigated. The capital cost and the operating labor and materials made this a last chance choice. Following work done in the metallurgical laboratory on the tailings return water, it was found that some changes in the reagent strengths and combinations made a very definite decrease in the solids in the pregnant solution. Concentrate grade improved about 5 pct anti the final product after drying had an appreciably greater bulk density. Compared to a cost of about 2.2e per ton for pre-coat filter opelation for cleaning just one circuit, flotation costs less than 1.0 per ton of ore for cleaning two circuits. While a pre-coat filter would do a more thorough job, the flotation does all that is required for either circuit. Gravity causes the froth produced to run back into the leach circuit. This does not appear to result in a build-up of objectionable slime. No extra manpower is required; the operators in the separate areas can observe the operation of the cells and mix the small quantities of reagents as needed. Normally the 66-in. Fagergren cell requires 15 hp per cell, but this very dilute slurry needs only 10 hp for both cells. Originally, a combination of the two Arquads mentioned previously served as frothers and promoters. As further testing

Jan 1, 1962

By Jean Howard

RECENT attempts to produce secondary recrystalli-zation in high-purity iron have given conflicting results. Coulomb and Lacombe1&apos;2 did not find it but Dunn and Walter3,4 did. The latter workers have stated that (100) [001] and/or (110) [001] orientations develop depending on the oxygen content of the annealing atmosphere. This Technical Note records results which are in agreement with Dunn and Walter in so far as it shows that secondary recrystallization can be produced in high-purity iron, but does not confirm that both types of orientation are obtainable. Similar observations have been made on chromium-iron and molybdenum-iron, although when this technique is used on 3 1/4 pct Si-Fe, both types are obtained as in the work of Dunn and alter.&apos; Pure iron strip was cold-rolled from sintered compacts prepared from Carbonyl Iron Powder-Grade MCP of the International Nickel Co. (Mond) Ltd. The powder contains about 0.5 pct 0, 0.01 pct C, 0.004 pct N, (0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni—that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The iron powder was (a) pressed at 25 tons per sq in. into blocks measuring 3 by 1 by 0.3 in., (b) deoxidized in hydrogen (dewpoint -60°C) by heating first at 350°C and then at 600° C until the dewpoint returned to -60°C at each temperature and (c) sintered in hydrogen (dewpoint -40°C) at 1350°C for 24 hr. (when dewpoint is referred to in this Note, it is the value as measured on the exit side of the furnace). The sintered compacts were cold-rolled to 1/8 in., annealed in hydrogen (dewpoint -60°C) at 1050°C for 12 hr and cold-rolled to 0.004, 0.002, and 0.001 in. with inter-anneals at 900°C for 5 hr and a final reduction of 50 pct. Final annealing of strip between alumina or silica plates at 875" to 900°C in hydrogen with dewpoints of -20°, -55" and -80°C produced secondary grains with the (100) in the rolling plane; the extent of secondary recrystallization was greatest when the dewpoint was -55°C. Annealing in a vacuum of 2 x 10"5 mm Hg at the same temperature produced no secondary recrystallization at all. With strip thicker than 0.002 in. very few secondary crystals developed whatever the conditions of annealing. Using a processing schedule somewhat similar to that described above, secondary recrystallization was produced in two bcc alloys of iron, viz. 80 pct Fe + 20 pct Cr and 96 pct Fe + 4 pct Mo. The former was reduced to final thicknesses of 0.001 to 0.004 in. and the latter to final thicknesses of 0.001 to 0.016 in. With the chromium-iron, a final anneal at 1250°C (found to be the most effective temperature for developing secondary crystals in the 0.004-in material) with a dewpoint of -25°C produced a greater degree of secondary recrystallization than with dewpoints of -50°C or -20°C. Secondary crystals developed in strips of all thicknesses from 0.001 to 0.004 in. Final annealing in vacuum produced no secondary crystals at all. For the molybdenum-iron a temperature of 1200°C was most effective. It was found that a dewpoint of -50°C during the final anneal gave better results than a dewpoint of -25 "C on the 0.008 in. material. Final annealing in vacuum gave slightly worse results than annealing in hydrogen with a dew-point of -50°C. Secondary crystals were developed in strips of all thicknesses up to 0.008 in. The experiments show that the extent of secondary recrystallization is a maximum for certain critical values of oxygen content of furnace atmosphere and annealing temperature, and that these values are different for different alloys. The thinner the material, the less critical these values are. The general conclusions are that secondary recrystallization can be obtained in high-purity iron, chromium-iron, and molybdenum-iron, using a processing schedule similar to that which will cause the phenomenon to take place in high purity 3 1/4 pct Si-Fe. Unlike the silicon-iron, however, only the (100) (0011-- orientation has been produced in these alloys, irrespective of the temperature of final annealing and the oxygen content of the furnace atmosphere. The information used in this Note is published by permission of the Engineer-in-Chief of the British Post Office.

Jan 1, 1962

By David A. Thomas, David N. French

The lrnrdness of WC crystals has been measured with the Knoop indenter at loads of 100 and 500 g on the (0001) and (1070) planes. The hardness as tneasitred on the basal plane is 2400 kg per sq mm and shows little anisotropy. The hardness on the prism plane, however, shows a marked orientation dependence, with a low value of 1000 kg -per sq mm when the long axis of the Knoop indenter is oriented parallel to the c axis and a high value of 2400 kg per sq mm when the indenter is perpendicular to the c axis. Slip lines (Ire observed surrounding the microhardness indentations and they show slip on (1010) planes, probably in [0001] and (1120) directions. This slip behavior can be explained by the crystal structure of TVC, which is simple hexagonal with a c/a ralio of 0.976. The hardness anisotropy call be explained by [0001]{1010} and (1130) {10l0] slii) and the resolved shear-stress analysis of Daniels and Dunn. HARDNESS anisotropy is a well-known phenomenon and has been reported for many metals, with both cubic and hexagonal structure.1-6 For hexagonal tungsten carbide, WC, a wide range of hardness values is reported in the literature. For example, Schwarzkopf and Kieffer7 give a hardness of 2400 kg per sq mm and report a value of 2500 kg per sq mm by Hinnüber. Foster and coworkerss give the average Knoop microhardness as 1307 kg per sq mm with a maximum value of 2105 kg per sq mm. Although these values and the structure of WC suggest the likelihood of hardness anisotropy, no such measurements have been made. We first detected a large apparent hardness anisotropy in WC crystals about 75 p large, in over-sintered cemented tungsten carbide. Prominent slip lines also occurred around many indentations. This report presents further observations and interpretations of hardness anisotropy and slip in WC crystals obtained from Kennametal, Inc. Both Knoop and diamond pyramid indenters were used on a Wilson microhardness tester with loads of 100 and 500 g. EXPERIMENTAL RESULTS The carbide crystals tended to be triangular plates parallel to the (0001) basal plane of the hexagonal structure. The side faces were parallel to the ( 1010) prism planes. Specimens were mounted approximately parallel to these two types of faces and metallographically polished. Laue back-reflection X-ray patterns were used to orient the specimens, which werethen ground to within ±1 deg of the (0001) and (1010) planes. The Knoop hardness values measured on the basal plane are plotted in Fig. 1. There is only a small anisotropy, with a hardness range of 2240 to 2510 kg per sq mm. The additional points at angles from 52.5 to 67.5 deg confirm the sharp minimum hardness at 60-deg intervals, consistent with the sixfold hexagonal symmetry. The average hardness of all values obtained on the basal plane is 2400 kg per sq mm. While the basal plane shows only slight anisotropy, the (1010) plane exhibits marked hardness anisotropy, from 1000 to 2400 kg per sq mm. Fig. 2 shows the hardness as a function of the angle between the long axis of the indenter and the hexagonal c axis, the [0001] direction. The minimum and maximum occur when the indenter is oriented parallel and perpendicular to the [0001] direction, respectively. The anisotropy of the prism plane is contrary to that reported for hexagonal zinc and hard- However, the basal-plane anisotropy is similar to these two metals.1&apos;2 To check the accuracy and reproducibility of the measurements, a series of fifteen impressions was made at 100-g load in the same orientation in the same area of the specimen surface. The average for all was 2040 kg per sq mm, with a range of 1950 to 2130 kg per sq mm, giving an accuracy of about ± 5 pct. Thus the slight anisotropy on the basal plane is almost within experimental error. Fig. 3 shows slip lines around the Knoop indentations on the basal plane. The slip traces are in directions of the type (1130). The presence of slip steps on the basal plane indicates that the slip direction lies out of the (0001) plane. Because WC has a c/a ratio of 0.976,&apos; the shortest slip vector is [0001], which suggests slip systems of the type [0001] (1010). Fig. 4 shows slip lines around the Knoop intentations on the (1010) plane. These slip lines are inconsistent with [0001] slip but can be

Jan 1, 1965