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By Jack L. Taylor

WITH the exception of the work of Vogel,&apos; and Rolla and Iandelli, very little information has appeared in the literature on titanium binary systems with the rare earth elements. Rare-earth additions to titanium alloys may possibly parallel the beneficial effects on the physical properties of certain steels. Having this in mind, some knowledge of solubility limits and intermediate phases, if any, would be useful. An investigation of the titanium-rich Ti-Ce system was started. Alloy Preparation The iodide titanium from the New Jersey Zinc Co. and the cerium metal from the Institute for Atomic Research Ames Laboratory used in this work were supplied with the typical analysis shown —iodide titanium: 0.0065 pct Mn, 0.0022 pct Fe, 0.0015 pct Cu, and 0.0042 pct Pb; cerium metal: <0.01 pct Fe, <0.03 pct Si, <0.05 pct Ta, <0.02 pct Pr, <0.03 pct Ca, <0.02 pct Mg, with no trace of Nd, La, or Th. The cerium metal, stored in oil, was washed and scraped just before weighing into capped cups machined from iodide titanium. The cold hearth helium-arc furnace described by Schramm et al3 was used for melting. The alloy buttons from the arc-melted cup were cut in two, mounted, and examined. Homogeneous alloys were demounted and rolled to approximately 1/4-in.sq bars. Sections l/8 in. thick were cut from the bar to provide samples. The Ti-Ce alloy buttons analyzed for cerium were of the following composition: 0.19, 0.36, 0.48, 0.61, 1.15, 2.52, 3.06, 3.70, 4.30, 9.20, 14.26, and 18.50 wt pct. Nominal

Jan 1, 1958

Donald H, McLaughlin San Francisco, Calif PAST PRESIDENTS W E Wrather, Washington, D C L E Young, Pittsburgh, Pa VICE-PRESIDENTS C Harry Benedict, Lake Linden, Mich A B Kinzel, New York, N Y Philip Kraft, New York, N Y C V Millikan, Tulsa, Okla RoRobert W Thomas, Boy, Ariz VICE-PRESIDENT AND TREASURER Andrew Fletcher, New York, N Y

Jan 1, 1952

By R. L. Skaggs, D. T. Peterson

The effect of carbon in solid solution on the plastic behavior of thorium was studied by measuring the flow stress of Th-C alloys from 4.2" to 573°K and at several strain rates. Carbon was found to strengthen thorium primarily by increasing the thermally activated component of the flow stress. The strengthening due to carbon was directly proportional to the carbon content and decreased rapidly with increasing temperature up to 423" K. The flow stress also increased with increasing strain rate. The strengthening appears to be due to a strong short-range interaction between carbon atoms and dislocations. A yield point was observed in the Th-C alloys which increased with increasing carbon content. JTREVIOUS study of the mechanical properties of thorium has been confined largely to the measurement of the engineering properties. Work prior to 1956 has been summarized by Milko et al.1 who reported that additions of carbon to thorium sharply increased the room-temperature strength. In addition, the yield strength was observed to decrease rapidly over the temperature range from 25" to 500°C. In 1960, Klieven-eit2 measured the flow stress of thorium containing 400 ppm C. He found that over the temperature range from 78" to 470°K the flow stress was strongly dependent on temperature and rate of deformation. A drop in the load-elongation curve, or a yield point, was observed over most of the above temperature range. Above 470°K, the flow stress was nearly independent of temperature and strain rate. This strong temperature and strain rate dependence of flow stress is not generally observed in fcc metals. It is, in fact, more typical of the behavior reported for bcc metals. Bechtold,3 Wessel,4 and conrad5 have pointed out the striking difference between the commonly studied bcc metals and fcc metals in regard to the effect of temperature and strain rate on the flow stress. Zerwekh and scott6 studied the plastic deformation of thorium reported to contain 12 ppm C. They found that this material did not obey the Cottrell-Stokes law as expected for fcc metals. In addition, they found values of the activation volume smaller by an order of magnitude than expected for an fcc metal. They concluded that thorium was strengthened by a randomly dispersed solute. Thorium differs from many other fcc metals that have been studied extensively in that it shows a relatively high carbon solubility at room temperature. Mickleson and peterson7 report the solubility limit at room temperature to be 3500 ppm C. The lowest value reported is that of Smith and Honeycombe8 who report the limit to be 2000 ppm C at 350°C. The pres- ent investigation was a systematic study of the flow stress and yield point phenomenon of thorium over a broad range of carbon content, temperature, and strain rate. EXPERIMENTAL PROCEDURE The thorium used in this investigation was produced by the reduction of thorium tetrachloride with magnesium as described by Peterson et a1.&apos; Chemical analysis of the original ingot after arc melting and electron beam melting is shown in Table I. Alloys were prepared by arc melting this thorium with high-purity spectrographic graphite. Threaded specimens with a gage length 0.252 in. diam by 1.6 in. long were used for the constant stress or creep measurements. These specimens were machined from rod which had been cold-rolled and swaged to % in. diam. Tensile specimens were prepared by swaging annealed 3/8 -in.-diam rod to 0.102 *0.001 in. The as-swaged wire was cut to lengths of 2 in., annealed, and the center 1-in. gage length elec-tropolished to 0.100 ±0.001 in. The specimens were gripped for a length of 3 in. at each end by a serrated four-jaw collet which was tightened by a tapered compression nut. No slipping occurred in the grips and negligible deformation was observed outside the 1-in. gage length. Both the creep and tensile specimens were annealed at 730°C under a vacuum of 1 x X Torr. The resulting structures consisted of equiaxed recrystallized grains with a grain size of 3200 grains per sq mm for the tensile specimens and 2200 grains per sq mm for the creep specimens. After the specimens were prepared, samples were analyzed for nitrogen, oxygen, and hydrogen. The results of these analyses are given in Table 11.

Jan 1, 1969

By A. L. Holley

IN order to put sufficient work on steel ingots for rails, they must be reduced from about 12 inches square. As this cannot be done at one heat, they are first drawn down to about 7 inches square, and then reheated and rolled into rails. This first reduction or " blooming," is usually done in this country in a 30-inch 3-high rolling-mill, with movable rolls, so as to get several reductions in each set of grooves. The first of these mills has been running at the Troy Steel-works above a year, with great success. Another at the Cambria Iron-

Jan 1, 1873

By S. Nenno, T. Saburi, Y. Mizutani, M. Yomarnoto, K. Komatsu

In the equilibrium phase diagram of the Ni-Mo sys-tem1,2 available at present, intermetallic compounds (or ordered phases)ß(Ni4Mo) and ?(Ni3Mo) are known to exist to the nickel rich side. In our recent investigations on Ni-Mo alloys, however, it has been found that the quenched alloys from the high temperature region containing more molybdenum than the Ni4Mo do not decompose directly into 0 and when annealed isothermally below the peritectoid temperature, i.e., 865°C. This note is to report the existence of Pt2Mo type superlattice (possibly ordered Ni2Mo) as a metastable phase in the early stage of decomposition. Alloys containing 20.1, 22.7, and 24.4 at. pct Mo were prepared by vacuum-melting electrolytic nickel of 99.9 pct purity and molybdenum powder of 99.9 pct purity in an alumina crucible. From the resulting ingots, sheets 0.3 mm thick were obtained by forging, hot-, and cold-rolling. The sheet specimens were water-quenched from ! region and subsequently annealed for various periods of time at temperatures below the peritectoid temperature. On these specimens were made optical-microscopic and transmis-sion-electron-microscopic observations. Fig. 1- Optical micrograph of the 22.7 at. pct Mo specimen annealed for 100 hr at 700°C after quenching. (ß + ?) region, B, nucleated along a grain boundaries are invading the preexisting (ß + Ni2Mo) region, A. Details of A are observable only by electron microscopy. Etchant: 60 pct HNO3-40 pct CH3COOH.

Jan 1, 1970

By R. A. Burton, J. T. Hansford, D. A. T. Donohue

Substantial evidence indicates that many petroleum producing horizons contain naturally occurring, ordered fracture systems and that within a particular geologic zone, vertical fractures induced in wellbores often will be directed along a particular compass direction. Both conditions will seriously alter the fluid displacement behavior within reservoirs. In this study the effect of induced fracture orientation and length on sweep efficiency is determined for a five-spot pattern. In general, it is assumed that all wells are fractured and directed along the same compass direction. Using the electrical analog to steady state, two-dimensional fluid flow in porous media, boundary conditions are obtained from which flood fronts are tracked numerically. The numerical computations require a particle tracking routine for approximating flood front histories. It is shown that recovery is sensitive to the length and orientation of fractures for the pattern studied. with the proper design of fracture-pattern systems, recovery can be enhanced considerably. INTRODUCTION Hydraulic fracturing introduced in 1949l gave the industry a rather inexpensive means of increasing the fluid injection or production capacity of wells. It has been used with particular success to increase the production rate of wells completed in tight formations, such as in western pennsylvania2 where producers have fractured in depleted or near-depleted fields and observed economic responses. Once the natural energy declines in such a reservoir where all wells have been fractured, waterflooding is generally suggested as means of further increasing recovery. Of the dual objective sought in waterflooding — high injectivity and high breakthrough sweep efficiency — the former condition can be obtained if all wells in the flood pattern are fractured; the latter condition should depend on the nature of the fracture system. Considerable theoretical work has been published on the nature of fractures induced in boreholes.3-5 Although discussion persists concerning the possibility of forming a horizontal fracture at a given point within the wellbore, it is generally conceded that only vertical fractures will develop below a given depth, i.e., where the fracturing Pressure is less than the overburden load. Given the fact that fractures will be vertical in most cases of interest, it is also important to know whether there is order to fracture orientations within a given geological region. Kehle has suggested that in tectonically relaxed areas of uncomplicated geology, the stresses are fairly uniform and all fractures in the region should be parallel.5 Dunlap arrived at a similar conclusion in a theoretical investigation of localized stress conditions surrounding the borehole.6 He concluded that most vertical fractures are propagated in a preferred azimuthal direction. Fraser and Pettitt, in extending these theoretical suggestions to a specific field case, used an impression packer to record both a vertical fracture and the orientation of this fracture in the wellbore of a well in the Howard Glasscock field, Tex.7 Use of this information enhanced the waterflood recovery of the field. Anderson and Stahl also used impression packers on three fractured wells in the Allegheny field. N. Y.. and found that the fractures were oriented more or less along the same compass direction.8 Orientation of the fractures in this manner depends on the stress condition within the formation during fracturing. Elkins and Skov have demonstrated that a natural, oriented, vertical fracture system exists within the Spraberry field? Heck suggests

Jan 1, 1969

INDUSTRIAL MINERALS DIVISION (Nonmetallics) Established as a Division March 15, 1935 Ian Campbell, Chairman Robert C Stephenson, Eastern Vice-Chairman Allen Cole, Southeastern Vice-Chairman David P Hale, Jr, Rocky Mountain Vice-Chairman G H Waterman, Western Vice-Chairman M F Goudge, Canadian Vice-Chairman James Norton, Secretary-Treasurer Mineral Deposits Branch U S Geological Survey Washington 25, D C.

Jan 1, 1952

Manganese ore from the Black Rock, Kramer, and Black Jack mines in Tooele and Jaub Counties, Utah, are of acceptable grade, the U. S. Bureau of Mines has announced. Payment of a premium price of 252¢ per lb to the Copper Range Co., of Michigan for the output of its White Pine mine, has been agreed to by the DMPA. The contract will be limited to $28.6 million worth of copper. The agreement follows an RFC loan grant of $57 million to bring the White Pine property into production within three years. Increases of 5 to 6 cents over the Lake copper ceilings have been granted to the Calumet & Helca Consolidated Copper Co., for operation of "high cost" deposits, according to Jess Larson, DMPA administrator. Mr. Larson expects the move to add about one million lb of copper per month to the supply. The agreement can be cancelled on 60 days notice and is terminated automatically in the event copper ceilings are removed.

Jan 1, 1952

De la pirotechnia. Libri .X. dove ampiamente si tratta non solo di ogni sorte & diuersita di miniere, ma anchora panto si ricerca intorno á la prattica di quelle cose di quel the si appartiene á l&apos;arte de la fusion ouer gitto de metalli come d&apos;ogni altra cosa simile I questa. Composti per it S. Vanoccio Biringuccio]

Jan 1, 1942

By Sir Robert Hadfield

Table 1 gives the composition of the specimens listed by the author. The details of test procedure and the results of the tests on mechanical, magnetic and electrical properties and cor-rodibility of the alloys are published in full in a paper by the same author, "Alloys of Iron and Manganese Containing Low Carbon," presented before the Iron and Steel Institute (of Great Britain) and published in full in their Proceedings for 1927, to which reference should be made. After reporting these tests the author gives the following discussion of results:] The studies here reported do not indicate that any of the series has really valuable or useful qualities for industrial applications, though the demands of industry are so varied that it is unsafe to prophesy that no special use will be found for a given material. The non-magnetic property of manganese steel is due to the association of Fe and Mn, but carbon has also an effect, enabling non-magnetic qualities to be obtained with a much lower percentage of Mn than would otherwise be the case; for example, 16 per cent. Mn is necessary for alloys practically free from carbon, while with 1 per cent. C nonmagnetic alloys may be obtained with as little as 7 per cent. Mn. Carbon, however, is the prime cause of the development of magnetic qualities by heat treatment. (Sec section 8 of the paper referred to above.) These Fe-Mn alloys show a resistance up to 87 microhms per c. c., but. as there are other alloys which have a resistance as high as 130 microhms per C. c., this does not provide any new feature of value. The most marked feature of the series studied is the brittleness in the range 3 to 10 per cent., with a maximum of brittleness at 7 per cent. Material with this percentage, while possessing quite appreciable hard-

Jan 1, 1927

By P. Lelong, P. Lacombe, J. Herenguel

IN previous studies on the effect of orientation on the rate of anodic oxidation of A1-3 pct Mg mono-crystals of high purity, certain anomalies were observed on the cold-worked metal. These anomalies were shown to correspond to regions of changed orientation within the grains resulting from plastic deformation.&apos; In fact, they are deformation bands revealed by differences in rate of oxidation and produced by more or less continuous bending of the lattice about a [Ill] axis common to the original crystal and the band.2,3 Preliminary observations made after relatively large degrees of cold working revealed an approximate twin relationship between the bands and the surrounding crystal. Fig. 1 shows the etch figures formed on such a band and on the original monocrystal after a 67 pct rolling reduction. It is evidently not a true twinning, since there is a broad transition zone between the two systems, however the two extreme orientations are nearly in a twin relationship. It was decided to investigate these preliminary observations by progressive rolling-reductions on monocrystals of varied initial orientation. From these studies, which form the subject of the present article, it became apparent that the initial observation of an approximate twin relation between the bands and the monocrystal was simply a special case. Our experiments show that deformation in rolling proceeds by a mechanism analogous to those which have already been observed in the simpler cases of tension and compression. Micrography—in particular, the formation of etch figures—has been applied to the quantitative study of these orientations. In addition, observations have been made of slip lines, of thin oxide films yielding interference colors, of thick films in polarized light, and of etchants giving "engraving." These micrographic methods for studying orientation have established the orientation relationship without any ambiguity, whereas X-ray methods would have given only a statistical result because we were often dealing with thin bands (2 to 100 microns) and even narrower connecting zones covering a maximum of 20 microns. Specimen Preparation and Methods The Al-3 pct Mg alloy was prepared from 99.95 pct A1 and is of the type used industrially in France for brilliant anodized finishes under the name of Brillalumag. This material combines the normal commercial properties with an enduring brilliance due to the protection of a thick, but perfectly transparent, film of alumina.&apos; The monocrystals were prepared by the method of critical deformation followed by prolonged annealing. Great care was taken to insure perfect homogeneity of composition, to eliminate included crystals,6,7 and to avoid the formation of undulations during oxidation. The critical deformation for this alloy is about 1.2 pct (1-l0/10x100) and the subsequent annealing was for one week at 500 °C after gradual increase of temperature (35°C per hr). The crystals thus prepared had a section of 10x5 mm and a length of 20 to 40 mm. Each of these crystals was polished electrolytically and etched for the formation of etch-figures with the classical reagent.&apos; The orientation was then calculated from their angles, as measured with a goniometer microscope.

Jan 1, 1954

By J. B. Cohen, S. L. Sass

The nucleation process for y&apos;, Ni3Ti, is shou&apos;n to change from heterogeneous to uniform as the undercooling within the phase boundary increases. As unifornz nucleation beconres copious, (100) alignment is observed in the early stages of aging; howecer. whether or not the alignment is due to spinodal decomposition could not be determined. The presence oi a large-scale reversible segregation of titanium and not the intermediate precipitate y&apos; may be the cause of the initial strengthening in this alloy system and the discrete regions detected magnetically by Ben-Israel and Fine. Evidence is presented for the role of dislocations in the formation at long aging tines oJ the equilibrium precipitate . ThE nickel-rich portion of the Ni-Ti phase diagram consists of a terminal fcc solid solution of titanium in nickel called y.&apos; For temperatures below 1290°C if the solubility limit is exceeded and the temperature is high enough, the excess titanium will combine with nickel to form q, Ni3Ti, a four-layer hcp ordered structure with stacking sequence ABAC."~ Since a change in structure is involved, formation of q is slow and a metastable precipitate referred to as y&apos; forms. This metastable precipitate is an ordered cubic phase in the unconstrained state having a structure similar to Cu3Au (LIZ) with the composition Ni,Ti."&apos;5 From X-ray studies,8, 7 the following sequence is indicated for the precipitation reaction at low temperatures: 1) The appearance of satellites around low-index diffraction spots and splitting of high-index spots, indicating the formation of a slightly tetragonal phase in an imperfectly periodic arrangement. The tetragonal phase is y&apos; or the depleted matrix, depending on the volume fractions of matrix and precipitate (and hence, the alloy composition); tetragonality apparently arises from coherency strains. 2) The appearance of diffraction spots from the equilibrium second phase, q. Ben-Israel and Fine&apos;" used magnetic methods to measure the changes in matrix composition during aging, and to estimate the precipitate composition in a Ni-10.1 at. pct Ti alloy. They observed that the alloy, solution-treated at 1270°C and quenched, contained heterogeneities with discrete compositions which gradually vanished upon aging. It was suggested that y&apos; may initially form as a defect structure with several possible compositions deficient in titanium as compared to Ni3Ti; the composition Ni3Ti develops with prolonged aging. The initial composition was Ni6Ti which would require a very large deviation in stoichiometry for y&apos;. It was noted that at 700°C the precipitation reaction was 80 pct complete after 2 hr and that the volume fraction of second phase was 0.2 after 1 hr. Mihalisin and Decker&apos; suggested that the equilibrium precipitate, besides being nucleated at grain boundaries, could also form at stacking faults. ~errick" examined the formation of in Ni-Cr-Ti, and suggested that a collapsed vacancy cluster within y&apos; acted as a nucleus for intragranular q at high temperatures, 820" and 900°C. After long aging times at lower temperatures, 650" and 750°C, diffraction patterns taken from regions containing ribbons of stacking faults showed spots associated with q. Aging greatly enhances the mechanical properties of these alloys, even at high temperatures, and the metastable precipitate y&apos; is thought to be responsible.&apos; At 600°C the hardness of a Ni-10.1 at. pct Ti alloy increases rapidly during the first 20 hr of aging and continues to increase slowly thereafter.&apos;" At 700°C the hardness reaches a maximum at 1 to 2 hr and then decreases.l1 In this paper the kinetics of formation of y&apos; and the mechanism of transformation to in a Ni-Ti alloy are described. Evidence is presented that suggests that large-scale regions of titanium segregation are present initially and these may have an important influence on the initial strengthening of the alloy: these regions may be the heterogeneities detected by Ben-Israel and Fine. I) EXPERIMENTAL TECHNIQUES The Ni-10.3 at. pct Ti-0.6 at. pct A1 alloy was prepared by vacuum melting. Its chemical analysis is given in Table I. A 0.007-in.-thick strip was sandwiched between foils of the alloy and placed in an open Vycor tube with titanium chips (to get oxygen) and solution-treated for ; hr at 1150°C in a Globar Furnace under a flowing argon atmosphere. Following a quench into an ice-brine mixture at -5" to -2"C, a sample to be aged at temperatures up to and including 700°C was sealed in an evacuated Vycor capsule before being put into a fused salt bath. Aging above 700°C was carried out on bare samples in a salt bath. When removed from this bath and quenched into an ice-water mixture, the sample was normally coated with a thin layer of oxide easily removed with emery

Jan 1, 1970

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;&apos;,&apos; however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3&apos; The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962

Coal Division Industrial Minerals Division Minerals Beneficiation Division Mining, Geology and Geophysics Division Elmer A Jones, President President-elect Will Mitchell, Jr, Past President J B Morrow, Eastern Regional Vice-President G Donald Emigh, Central Regional Vice-President J D Forrester, Western Regional Vice-President R B Ladoo, Treasurer John Cameron Fox, Secretary AIME 29 West 39 St, New York 18, N Y

Jan 1, 1957

By R. E. Old

THROUGH the use of pressure and production records, formation properties and bottom-hole sample data, the performance of an oil reservoir may be studied analytically to define and evaluate the natural forces acting on and within the reservoir. Use is made of material-balance methods and the equations for natural water encroachment to estimate reserves. Methods for calculation of pressures are given. A study of the Jones sand, Schuler field, Arkansas, has been made and is given here to illustrate the value of the methods discussed.

Jan 1, 1942

By Wayne C. Hazen, James K. Kindig

As the complexity of hydrometallurgical systems increases, it offers new opportunity for applications of solvent extraction. However, the high capital cost of mixer-settlers for large flow rates is a drawback to wide application in base metal recovery. This paper presents information on the use of cyclone separators in place of settlers with attendant significant reduction in capital cost. Various flowsheet possibilities for this development are discussed.

Jan 1, 1972

By J. R. Hornaday, A. E. Morris, N. A. Parlee, D. C. Carmichael

Rates of absorption and effusion of hydrogen in solid iron were measurede by a Sieverts type of apparatus. With clean a iron these rates are diffusion controlled down to 420°C and are represented by the equation D = 6.70 x e-&apos;100&apos; crn2 sec-I Certain surface impurities can affect these rates at all temper-atuves. Thin oxide films lower, the apparent diffusivity of annealed iron markedly. Cold-worked iron (75 pct) annealed at 430°C has practically the same solubility and diffusivity as anealed iron. THE mechanism of absorption and evolution of hydrogen in solid iron alloys is not fully understood despite the large number of investigations on the subject. While there appear to be many instances of simple solid-state diffusion control of rate, there are many cases where investigators have either concluded that surface reactions are rate controlling or that some "nondiffusible" hydrogen resides in discontinuities. The purposes of this research were 1) to develop a sound method for studying this absorption and evolution behavior, 2) to examine it in pure annealed iron, and 3) to determine the effects of important variables, such as cold work, surface condition, and composition. This paper relates the progress toward these objectives. Much of the present knowledge of the movement of hydrogen through iron alloys comes from permeability studies which involve the measurement of the rate of passage (under steady state conditions) through membranes of the order of 1 mm in thickness. This method is open to question on various grounds. If surface reactions are involved, two different surfaces operating under two different conditions must be considered. The presence of defects in the membrane even of microscopic dimensions may lead to erroneous results. A few people have studied evolution of hydrogen into vacuum, under carefully controlled (unsteady state) conditions, and some of the best diffusivity data come from these sources. Most of these methods measure rates of evolution only and thus do not make a rigorous test for reversibility of behavior. It appeared that an "unsteady state" method that would permit the measurement of both rates of evolution and absorption under controlled temperature, pressure, and other conditions would offer several advantages. Accordingly the modified Sieverts apparatus described below was designed and built. APPARATUS This apparatus is shown in Fig. 1. The sample bulb is detailed in Fig. 2. Hydrogen of 99.5 pct purity and argon of 99.99 pct purity were used. The hydrogen was deoxidized and dried by means of a Deoxo unit followed by a "Dri-erite" tower. The argon was only dried. The gas burette was graduated in tenths of a cubic centimeter, and, with the aid of a travelling magnifier, readings could be estimated to the nearest 0.01 cc. The level of mercury in the burette was adjusted by means of a leveling bulb operated by a fine screw adjustment. An electrical system, consisting of two slightly separated platinum electrodes inserted in one leg of the manometer and a small light bulb was used to obtain rapid accurate adjustment of the pressure. The capillary tubing of the Vycor sample bulb was 3 mm bore as was all tubing back to the gas burette. The samples were discs made from vacuum-melted Ferrovac-E iron of greater than

Jan 1, 1961

By Robert C. Linares

Cubic zinc sulfide has been grown from molten salt solutions substantially below the hexagonal-cubic phase transition of 1020°C. Crystals free of birefringence have been grown from molten lead chloride at temperatures from 500° to 800°C. Factors affecting the optical transmission and the birefringence are discussed. CUBIC zinc sulfide is of interest for electrooptic devices and as an optical coating material. However, it cannot readily be produced as large crystals which are free of birefringence. The birefringence arises from the fact that the cubic ZnS is usually grown as the high-temperature hexagonal phase and is transformed to the lower cubic phase by annealing.&apos; This results in stacking faults, stress, and birefringence. A requirement for the growth of cubic ZnS is that it be grown below the phase transition of 1020°C.2 Crystals of cubic ZnS have been grown below 1020°C by the hydrothermal,3 flux,4 and vapor transport5 techniques. However, these all appear to have limitations in size or quality of material produced. It was felt that a new flux method might have a good chance of overcoming some of the previous problems. Mita6 reported the growth of hexagonal ZnS from molten NaCl and wilke7 reported the growth of iron sulfides from molten lead chloride solution, indicating that molten chlorides make good solvents for sulfides. An investigation of a number of possible molten chlorides as solvents showed that molten PbCl2 has an appreciable solubility for zinc sulfide and that crystals can be grown at temperatures from 500° to 800°C. EXPERIMENTAL Crystal growth was performed in open or sealed Vycor or fused silica tubes, in an argon atmosphere or vacuum. There were no deleterious effects due to using vacuum; however, a sealed essentially isothermal system must be used to prevent vapor transport mechanisms from dominating. This will be discussed later in detail. Noble metal containers were not usable as they were severely attacked by these melts. The materials used were: reagent-grade PbC12, reagent-grade ZnS, optical-coating-grade ZnS, and Irtran 2 (ZnS). Crystal growth was accomplished by both slow cooling techniques and gradient growth techniques. In the slow cooling techniques, 15 g of ZnS and 100 g of PbCl2 were used. The components were placed in the silica tube, heated at 800°C for 2 hr, and then slowly cooled (l° to 10° C per hr) to 500°C. The furnace was constructed so that the tube could be inverted, thus allowing the liquid to drain off the crystals at the end of the run. The gradient runs were made by placing the above mixtures in a silica tube at 550° to 600°c, Fig. 1. A temperature gradient was maintained such that the floating mass of undissolved sulfide was 10° to 50°C warmer than the bottom of the tube. Growth occurred on spontaneously nucleated sites at the cooler bottom. RESULTS When using high cooling rates (5° to 10°C per hr), crystals form in thin sheets perpendicular to the {111} face. Crystals 5 by 5 by 1.2 mm, Fig. 2, have been ob-

Jan 1, 1969

By I. J. Hegyi, J. J. Tietjen, H. Nelson, J. I. Pankove

The fabrication of p-n junctions in GaAsl-,P, alloys by a vapor-phase gowth technique has for the first tirne resulted in room-temperature injection lasers capable of operating over a broad range of wavelengths extending into the visible region of the spectrum. The shortest wavelength achieved to date is 6750A at room tetnperature. In addition, at 78°K the threshold current density values for these lasers are generally the lo~vest reported, and the emitted radiation extends to the lozc,est wavelength ever attained (6350A). With lasers fabricated from material containing 14 pct Gap, quanticm efficiencies of 26 pct and peak power outputs of 25 zu were obtained at room temperature. ALTHOUGH room-temperature operation of GaAs injection lasers has been well-documented,&apos;-5 the operation of GaAsl-,P, (x > 0) laser diodes has been restricted to relatively low temperatures.8-&apos;0 This has been previously attributed5, 7, 10-12 partially to the difficulty of preparing single-crystalline GaAsl-& alloys having a high degree of chemical homogeneity and purity. Also, with these materials it has been difficult to prepare high-quality, abrupt p-12 junctions by diffusion techniques; and, in turn, this has made it difficult to obtain optimum electrical properties for room-temperature operationL3 in the resulting laser diodes. As a result, GaAsl-,P, laser diodes have not been efficient enough to permit operation at room temperature. For example, using diffused structures, only a few diodes were obtained which could be operated even close to room temperature (255K)." Recently, a vapor-phase growth method of preparing epitaxial deposits of GaAsl - .P, alloys has been described,14 and the high-purity and homogeneity of these materials has been previously demonstrated. Of special significance, with this technique, n- or p -type doping can be initiated or discontinued at any time and at almost any rate during the crystal growth so that the donor and the acceptor concentrations can be easily controlled to obtain desired impurity profiles. This permits high-quality, abrupt p-TZ junctions to be vapor-phase grown entirely during the crystal growth process, so that diffusion or other p-n junction fabrication processes are unnecessary. After growth, the device does not have to be heated to elevated temperatures, which avoids the possible unwanted introduction and motion of both impurities and lattice defects. Using the vapor-phase growth method cited above, over 300 room-temperature injection lasers have been prepared from GaAsl-,P, alloys having compositions in the range of 0 5 x 5 0.41. These lasers have emitted cohe~ent radiation in the spectral range of 8350 to 6350A at 78°K or from 9000 to 6750A at room temperature. The threshold current densities of the best lasers are independent of the alloy composition over the range 0 < x < 0.2 and compare favorably with values for good GaAs lasers.&apos; MATERIAL PREPARATION Multilayer, epitaxial deposits of GaAsl-,P, alloys are prepared by a vapor-growth technique described elsewhere.14 With this technique, the individual layers which comprise the multilayer structure are prepared sequentially in the deposition apparatus without interrupting the crystal growth. The epitaxial layers are deposited on GaAs substrate surfaces oriented normal to the ( 100) direction. The substrate wafers employed in this study were usually doped with tellurium to an electron concentration of approximately 2 x 10" per cu cm. To avoid strains, the first 10 to 15 p of the deposited material is uniformly graded from pure GaAs to the specific GaAsl- ,P, alloy composition of interest. The GaAsl - ,P, alloy growth is then continued to form a layer of constant composition having a thickness in the range of 25 to 75 p. Both the graded region and the layer of constant composition are doped with selenium to an electron concentration of about 2 x 10" per cu cm. The p region of the diode is then incorporated in the crystal by abruptly changing the dopant concentrations in the vapor phase to facilitate doping with zinc. This layer has a hole concentration of approximately 3 X 1019 per cu cm and typically is 50 p thick. DEVICE FABRICATION In general, the GaAs substrate and the region of graded composition are removed. Ohmic contacts are made to the n-type side by tin evaporation and to the p-type side by an electrodeless nickel deposition. This is followed by an electrodeless deposition of gold on both sides. The crystal wafer is then cleaved along (110) planes and sawed into rectangular parallelepipeds. Typical dimensions are 100 by 300 for the junction area and 100 µ for the diode height. The diodes are either soldered to a copper stud or pressure-mounted in a copper clip. RESULTS AND DISCUSSION Approximately 400 laser diodes having compositions in the range of 0.41 have been prepared by the method described above. Each laser was routinely tested at liquid-nitrogen temperature. The lasers were operated with l-psec current pulses at a repetition rate of 60 pulses per sec. The parameters of greatest practical interest are the photon energy or wavelength of the laser output and the threshold current density. Fig. 1 shows the variation of photon energy with alloy composition at 78°K. The composition was determined from the lattice constant of the material obtained by X-ray back-reflection measurements. Although there

Jan 1, 1968

"In the spring of 1927, six members of the American Institute of Mining and Metallurgical Engineers met for dinner at the Chemists&apos; Club in New York to discuss the possibility of setting up a committee within the Institute to further the current interest in the science of steelmaking. Attention&apos; to this subject had been crystallized by a symposium held by the Faraday Society in 1925. &apos; After a prolonged discussion, ranging from thermodynamics to slag conditioning, it was decided to approach the Institute with the request that a standing committee on "The Physical Chemistry of Steel Making" be set up. This committee proposed to promote scientific and practical papers on the subject, and was designed to cooperate with the Open Hearth Committee of the Institute in bringing scientific developments to the attention of open-hearth operators throughout the country... . "As the life of the [Physical Chemistry of Steelmaking] Committee lengthened and general interest in the technical phases of steelmaking grew, it became evident that there was a distinct need for a book that might serve the open-hearth interests to better advantage than standard texts whose scope is necessarily wide and whose detailed exposition of the open-hearth process is, therefore, somewhat limited. With this thought in mind, the Committee, after some years of consideration and debate, embarked on the venture of writing a manuscript on `Basic Open Hearth Steelmaking&apos;." The foregoing paragraphs, taken from the introduction by C. H. Herty, Jr. to the first edition, well describe the circumstances which led to the publication of "Basic Open Hearth Steelmaking" in the spring of 1944. The book consisted of nineteen chapters contributed by twenty-three authors and edited by the staff of Alloys of Iron Research and T. S. Washburn, B. M. Larsen, and J. S. Marsh with Frank T. Sisco as consulting editor. The Engineering Foundation and the Open Hearth Steel Committee of the Iron and Steel Division, AIME, made financial grants; steel companies and other organizations supported the publication by contributing time and expenses of staff members in their capacity as authors or editors. The volume was sponsored by the Seeley W. Mudd Memorial Fund and appeared under the

Jan 1, 1951