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By C. L. Magee, H. W. Paxton

PREVIOUS workersl'% ave found that as-quenched ferrous martensites can be plastically deformed at low stresses. They have also found that the stress to obtain small strains can be significantly increased by aging at temperatures up to 150°C. This behavior has been interpreted in two ways: 1) that the deformation at low applied stress is due to internal stresses and thus the aging phenomenon is due to relaxation of the internal stresses;' 2) that the microdeformation arises through the motion of unpinned dislocations and the aging process is the diffusion of carbon to the dislocations to pin them.293 In a recent paper,4 we have shown that under certain conditions the dominant microdeformation mechanism of as-quenched Fe-31Ni marten-site-austenite aggregates is the transformation of retained austenite. Our results on resistance changes during deformation and temperature dependence of the deformation also established that, at temperatures above 300° K, the microdeformation was not due to this transformation. The purpose of this note is to report results of experiments which indicate that explanation 1 is appropriate for this deformation. All results presented here are from conditions where transformation does not make a measurable contribution to the microplastic deformation, in Fe-31Ni-0.002C, or in Fe-29Ni-0.02C-0.25Ti. The experimental techniques that were used for measurement of the plastic deformation are described4 and analyzed5 elsewhere. Fig. 1 shows the microplastic response of 100 pct austenite at 300" and 350° K. The microplastic response of an austenite-martensite aggregate is also given in Fig. 1 and it is seen that, after formation of martensite, the initial plastic deformation occurs at lower stresses. Thus, the softness is not entirely due to retained austenite—the quenched structure can be deformed at lower stresses despite the fact that the macroscopic strength is significantly higher. A result which allows a distinction to be drawn between the alternative explanations for this behavior is derived from aging experiments on the low-carbon alloy containing titanium. We have previously shown4 that the presence of titanium in this alloy reduced the free carbon to a sufficiently low level that thermal stabilization of the austenite-martensite transformation was not detected. Despite this, Fig. 2 shows that the microplastic response is decreased by aging treatments. A similar aging effect in Fe-ZONi, with some titanium, has previously been reported by . Thus, carbon is not necessary for the aging process and explanation 2 is at best incomplete. Since internal stress relief can occur independently of carbon (any temperature dependence of the flow stress can result in decreased internal

Jan 1, 1969

Using a Jarrell-Ash "Compact" direct reading spectrometer, analyses were made of a wide variety of rocks ranging from acidic to ultrabasic types. Statistical evaluation suggests that accuracies comparable with the values obtained by the rapid chemical methods used by the United States Geological Survey will be obtained.The spectrographic method involves fusion of the rock with lithium tetraborate, strontium being incorporated in the flux as the internal standard. The resulting bead is ground with graphite and pressed into a pellet. The counts obtained on two standard pellets are used to correct for instrumental drift.Background readings are made at 4109 Å and corrections for background are made to all lines. Corrections for matrix interferences, both by chemical suppression and optical enhancement, are made. The three corrections of drift, background, and matrix are incorporated into one general expression which has been programmed on magnetic cards, each element requiring a separate card. The cards are placed individually into a desk top computer (an Olivetti Programma 101), which enables true counts to be calculated from the "readout" counts, and the element concentration is then obtained from computer-printed tables by referring to the appropriate value of true counts versus concentration. These tables were prepared by making a polynomial regression analysis of the spectrographic results from 50 standard and analysed samples, a curve of best fit being chosen for each element.The regression coefficients, usually of a fourth or fifth degree equation, together with other relevant data, were fed into a large computer, programmed to print out tables of concentration versus true counts. This technique enables the results obtained to be based on mathematically-derived values rather than on hand-drawn calibration graphs, giving greater inherent accuracy. The technique has been shown to give results of good accuracy and acceptable precision suitable for many geological and geochemical exploration programmes involving the analysis of many rock samples of different types.

Jan 1, 1969

By G. Nabi, W-K. Lu

Cylindrical specimens of natural dense hematite were reduced to magnetite at atmospheric pressure in H2-H2O mixtures of known composition over the temperature range 1084° to 1284°K. The rate of reduction was measured by the rate of movement of the interface between hematite and magnetite. The diffusion of gases through the gaseous boundary layer, the magnetite layer, and the interfacial chemical reaction were all considered in the interpretation of experimental data. The mass transfer coefficient through the boundary layer was calculated using accepted correlations. Values of the chemical reaction rate constant and the diffusivity of hydrogen in the magnetite phase were determined. THE present investigation is concerned with the reduction kinetics of natural hematite to magnetite by H2-H2O mixtures in the temperature range 1084" to 1284°K at atmospheric pressure. This reaction is the first step in the series of topochemical reactions in the process of reducing hematite to iron. Kinetic information of the simple steps such as hematite-magnetite transformation is necessary in order to have a better understanding of the complex processes of hematite reduction in iron-making. It also has direct industrial significance because magnetic roasting is one of the most important methods in benefication of lean ore.&apos; Although many technical papers have been published on the process of magnetic roasting and iron oxide reduction, very little information is available in the literature concerning the fundamental nature of hematite reduction to magnetite by reducing gases. Hansen et al.2 reduced the dense synthetic pellets of high-purity oxide in CO-CO2 mixtures and determined the reaction rate by weight-loss method. They were able to interpret most of their results by applying the interfacial area control theory developed by Mckewan.3 In contrast, Wilhelm and St. Pierre,4 who studied reduction of hematite to magnetite in H2-H2O mixtures by weight-loss method, stressed that the resistance of the porous magnetite layer to the diffusion of gases cannot be neglected in consideration of the overall reaction rate. In the present study the contributions of interfacial chemical reaction, diffusion of gases through the magnetite phase, and the gaseous boundary layer to the overall reaction rate will be considered. APPARATUS AND PROCEDURE Hematite Specimens Preparation. Natural hematite ore from Vermillon range of Northern Minnesota was selected for the present investigation because of its high purity and thermal stability. Chemical analysis of five samples gave the following average values: 67.52 pct total iron (96.62 pct Fe2O3, 0.28 pct FeO, 0.03 pct metallic iron), 2.53 pct SiO2, <0.07 pct MgO, 0.03 pct CaO, 0.05 pct combined mixture, 0.07 pct loss on ignition, and 0.34 pct other. Cylindrical specimens of 0.93 cm in diam and 2.7 cm in length were drilled from slabs of ore with a water-cooled diamond core drill. These specimens were heated to 1000°C and furnace-cooled. Specimens with silica pockets developed large cracks. The uncracked specimens were heated a second time, and their surfaces were carefully examined with a microscope. Those with hairline cracks or surface inhomoaenitv-- were rejected. Preparation of H2-H2O Mixtures. H2-H2O mixtures were prepared by the combustion of H2-O2, mixtures in a pyrex glass chamber in the presence of a catalyst. Alumina pellets coated with palladium, supplied by Englehard Industries, were used as the catalyst. Purified grades of hydrogen and oxygen were used which were repurified by usual techniques. Hydrogen before entering the combustion chamber was passed through an activated alumina H2O absorption bulb, with copper turning at the top. The cover of this bulb was not made pressure-tight so that any pressure development in the hydrogen line would cause the cover to blow off and also the copper turnings would act as a flame arrester in the case of a flashback from the combustion flame. Oxygen flow rates were measured with a bubble flow meter after purification with 1 pct accuracy. Hydrogen flow rates were measured by "precision wet test meter" and the amount of unburnt hydrogen was accurately measured by a bubble flow meter, after condensing water vapor in the gaseous stream. The Pyrex glass bulb contained concentric Vycor glass tubes as shown in Fig. 1. Oxygen was prevented from diffusing into the hydrogen line by threading platinum wire through pores at the combustion end of gas inlet tube. The glass bulb was heated with a Kanthal heating wire pasted in asbestos paper. The surface temperature of the bulb was measured with a thermocouple and adjusted to remain at approximately 350°C. The gaseous reaction chamber also served as a preheater for gases to avoid thermal segregation. The following sequence of operation was adopted. 1) Nitrogen was passed through the outer concentric tube to purge the catalyst bulb of oxygen. 2) Hydrogen was introduced through the inner tube until a steady flow was obtained. 3) Oxygen was then introduced into the nitrogen stream passing through the outer tube. 4) When combustion had commenced and a flame was visible over the platinum wire, the N2 was turned off.

Jan 1, 1969

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

By M. R. Tek, L. K. Thomas, D. L. Katz

Threshold displacement pressures are needed to determine how much overpressure can be used in storing natural gas. An experimental technique for determining threshold pressures by displacing water with gas from samples saturated with water is presented. Threshold pressures for eight low permeability samples were measured. Threshold pressure data obtained in this work, plus data on higher permeability samples reported in the literature, are correlated with porosity, permeability, surface tension and formation resistivity factor. Mercury injection pressures also were measured and correlated with air-water threshold pressures. Threshold pressures were found to be independent of time. An aerial photograph of gas emerging from the top of a core shortly alter its threshold pressure has been exceeded shows that the gas bubbles are uniformly distributed across the face of the core. Channeling will occur, however, when an increased gas phase permeability is reached, A porous medium can be re resealed alter its threshold pressure has been reached, provided it has not been desaturated below a fixed saturation. Its new threshold pressure will be lower than when the sample is 100 percent saturated with water. INTRODUCTION The degree of overpressure in excess of the discovery pressure that a gas storage reservoir can withstand is determined by the ability of its caprock to contain gas, providing the pressure does not exceed the structural limit of the reservoir. The retention of gas in a reservoir by a caprock saturated with water is a result of the capillary forces acting at the gas water interface. Without the presence of water in a caprock, gas would leak out of the reservoir at a rate determined by the permeability of the caprock to gas. The ability of a caprock to contain gas is expressed in terms of its threshold displacement pressure, which is defined as the minimum pressure needed to initiate the displacement of a wetting phase by a nonwetting phase from a porous medium 100 percent saturated with the wetting phase. The gas industry must be able to predict how much "overpressure" a gas reservoir can withstand before leakage occurs by gas displacing water from caprock overlying the reservoir. This is of economic importance since the storage capacity of a gas reservoir is proportional to its pressure. The discovery pressure for most reservoirs is found between the upper and lower limits1 shown in Fig. 1. Discovery pressures in excess of their hydraulic pressure gradient are attributed to the compaction of an isolated shale formation by the overburden.2.3 The lower limit of 0.433 psi/ft corresponds to the weight of the overburden, the gradient of the rock itself. Somewhere between

Jan 1, 1969

By D. C. Anderson

Utah Construction & Mining Co.&apos;s Lucky Mc mine is one of the major uranium producers in the United States. It is located near the geographic center of Wyoming in Fremont County. The climate is middle-latitude steppe, with an average annual precipitation amount of 10 in.; the temperature varies from 40º below zero to 100º above. The land surface is moundlike, rolling terrain, with sparse grass and sagebrush. The northern slopes of the higher ridges support a scattering of juniper and pi[n]ion growth. DISCOVERY The discovery was made by Neil E. McNeice, of Riverton, Wyo., on Sept. 13, 1953. After prospecting the area and staking a few claims, McNeice reported his findings to geologists of the Atomic Energy Commission (AEC), who immediately began preliminary studies of the numerous surface uranium exposures of the district. The discovery received widespread publicity, resulting in an intensive search for uranium throughout the region ; thousands of claims were staked. The AEC drilled several shallow holes near the discovery outcrop. Assays of cuttings from these holes confirmed the presence of a low-grade, oxidized uranium deposit. McNeice and his partner, L. A. Morfeld, tried to start a mining operation but were plagued by a lack of capital and technical know-how. They sought assistance from a Salt-Lake-City-based mining firm, the New Park Mining Co., engaged in underground base-metal mining in the Park City district of Utah. After a period of negotiations, New Park initiated activities that led to the forming of the original Lucky Mc Uranium Corp. The company started limited development drilling and mining operations in the summer of 1954, with the first ore production being shipped by truck to the Vitro mill in Salt Lake City. The mining

Jan 1, 1969

By Hawkins L. V, Seedsman K

A combined reflection seismic and magnetic survey off the south coast of New South Wales has revealed six distinct reflection horizons within the Lower Triassic- Upper Permian sequence, and has enabled the upper part of the Illawarra Coal Measures to be mapped in considerable detail. Large magnetic anomalies in the eastern half of the survey area appear to originate in the Gerringong Volcanic Sequence which forms the magnetic basement in this survey. Small residual anomalies in the western half of the area can be correlated with small scale faulting and folding in the uppert part of the Illawarra Coal Measures, as revealed by the seismic reflection survey. A synclinal axis striking at approximately 55¦ has been mapped near the western margin of the survey area, and areas of faulting and folding have been outlined by com- bined analysis of seismic and magnetic results.

Jan 1, 1969

By E. Mille, R. Geffken

The Mg-Si and Mg-Ge phase diagrams were rede-levtnined by thermal analysis, and the existence of a single congruent melting compound in each system was confirmed. The melting points of the two compounds Mg2Ge and ,Wg2Si were found to be 1117.4° and 1085.0°C respectively. The euteclics for the Mg-Ge system occur at 635.6°C (1.15 at. pcl Ge) and 696. 7°C (64.3 at. pct Ge); for the Mg-Si system the eutectics are at 6376°C (1.16 at. pct Si) and 945.6°C (53.0 al. pcl Si). The phase diagrams and known thermodynamic data were used to calculate activity values for both systems. The activities calculated for the Mg-Ge system agreed very well with those previously published. Partial molar enthalpy values for the Mg-Si systetn were calculated from the phase diagram for the composition region where no experimental values have been reported. THE phase diagram for any system is an important source of thermodynamic data. Steiner, Miller, and Komarek1 have derived equations which permit calculation of the activity in binary systems with an inter-metallic compound! if the liquidus and enthalpy data are known. The thermodynamic properties of the Mg-Ge and Mg-Si systems have recently been determined in this by by an isopiestic method, and it was considered that it would be interesting to compare these directly determined values with those computed from the phase diagram. The basic features of the Mg-Ge and Mg-Si systems are essentially similar. The one intermediate compound present in each system. Mg2X, crystallizes in the antifluorite structure and melts congruently. Raynor4 has accurately determined the temperature and composition of the magnesium-rich eutectic in both the Mg-Ge and Mg-Si systems. Klemm and West-linning5 investigated the entire Mg-Ge liquidus, employing sintered alumina crucibles; the purity of the magnesium and germanium starting materials was not reported. The melt was not stirred, and the temperature was automatically recorded to an accuracy of ±3°C. The authors reported large weight changes due to magnesium evaporation between 50 and 67 at. pct Mg. The Mg-Si system has been studied by a number of investigators, and the results have been compiled by Hansen and Anderko.6 Significant discrepancies exist between the two principle investigations of voge17 and Wohler and Schliephake.8 Two different grades of silicon were used by Vogel, one of 99.2 pct purity and the other quite impure, containing 6 pct Fe and 1.7 pct Al. The magnesium purity was not specified. The melts were contained in graphite crucibles with porcelain thermocouple protection tubes under an atmosphere of hydrogen. Samples weighing 10 g were rapidly heated to 50° to 100°C above the liquidus: held, and then rapidly cooled without stirring. Accuracy was ±1 at. pct which is equivalent to a maximum error in temperature of ±18°C. Wohler and Schliephake used 97.9 pct Mg and 99.48 pct Si. The graphite crucibles contained a stirrer and the 15-g samples were melted under an atmosphere of streaming hydrogen. The samples were chemically analyzed after each run. Because of the scarcity of the data, the impurity of the starting materials, and the resultant uncertainty and inconsistency in the published liquidus values, it was decided to undertake a reevaluation of the Mg-Ge and Mg-Si phase diagrams by thermal analysis. EXPERIMENTAL PROCEDURE Alloys were prepared from 99.99+ pct Mg (Dominion Magnesium Ltd.) with impurities in ppm: 20 Al, 30 Zn, 10 Si, <1 Ni, <1 Cu. <10 Fe; 99.999 pct Ge (United Mineral and Chemical Corp.), and 99.999 pct Si (Wacker Chemie Corp.). All graphite parts were machined from high-density (1.89 g per cu cm) G-grade graphite obtained from Basic Carbon Corp. with a total ash content of 0.04 pct. Boron nitride parts were machined from rods of National-grade H.B.N. boron nitride. All graphite and boron nitride pieces were baked out under running vacuum at 1100°C for 24 hr before us Cylindrical graphite crucibles (1; in. OD, 23/4 in. long, l3/8 in. ID) were tightly closed with threaded graphite covers which had 21/4-in.-long thermocouple wells and 1/4-in.-diam off-center holes for stirrers. The cover and thermocouple well were machined from a single piece of graphite. A stirrer was made from a flat cylindrical graphite plate perforated with five 3/16-in.-diam holes and a 1/2-in.-diam central hole, and was held parallel to the crucible bottom by a 1/4-in.-diam. 4-in.-long graphite rod which screwed into the plate and extended up through a tightly fitting hole in the crucible cover. An iron core enclosed in a glass capsule was attached to the stirrer with an 18-in.-long molybdenum wire, so that the stirrer could be magnetically raised and lowered from outside the system. One crucible and stirrer with essentially the same dimensions given above was made entirely of boron nitride. Chunks of magnesium were premelted, cast into 11/2-in.-diam. rods, and then cut into lengths varying from a to 1 in. A 5/16-in. hole was drilled through the center of each piece to accommodate the thermocouple well and the individual pieces were then cleaned and rinsed with acetone. The total weight of an alloy was 50 to 70 g in the Mg-Ge system and 40 to 60 g in the Mg-Si system. The pure components were weighed to an accuracy

Jan 1, 1969

By M. S. Seltzer

In a previous paper1 it was shown that activation energies for steady-state creep in lead sulfide single crystals varied with the concentration of electronic defects. For n-type lead-excess crystals, values for the creep activation energy, Qc, decreased from 2.9 to 2.2 ev as the carrier concentration increased from 1017 to 1017 electrons per cu cm, while Q, increased from 1.6 to 2.3 ev for p-type sulfur-excess crystals as the concentration of holes increased from 6 X 1017 to 1018 per cu cm. It was also shown in Ref. 1 that the Q, values could best be correlated with the sum of the self-diffusion activation energies in PbS, i.e., for a given concentration of electrons or holes Q, = QPb + Qs, where Qpb and QS are the activation energies for diffusion of pb210 and s35 in PbS. This result suggests that creep rates are controlled by at least two atomic defects, one for lead migration and one controlling sulfur transport. It would be most desirable to interpret these creep energies in terms of an atomic defect disorder model for lead sulfide. Studies of creep rates as a function of sulfur pressure2 indicate that the defects controlling creep rates are singly ionized lead and sulfur vacancies, VPb and Vs. This hypothesis can be more firmly established by determination of Q, under conditions of constant atomic defect concentration rather than constant electronic defect concentration as has been previously done. Therefore, several measurements have been made of Q, on crystals whose con- centration of lead vacancies or sulfur vacancies has been fixed by equilibration under appropriate sulfur pressure and temperature. It was indicated in Ref. 2 that high-temperature isotherms are available which show how the concentrations of various atomic point defects in PbS vary with composition over the entire homogeneity range for the compound. Two such isotherms are shown in Fig. 1 for 900" and 1000°K. Utilizing these isotherms the concentration of a given defect, say Vbb, may be held constant over a particular temperature range by adjusting the sulfur pressure as the temperature is changed. Thus the concentration of one defect suspected of controlling creep rates may be held constant while other defect concentrations vary. The apparent activation energy for formation of these defects can be obtained from the isotherms giving their concentration as a function of sulfur pressure. Activation energies for creep obtained under conditions of constant defect concentration can then be compared with defect formation energies and certain possible atomic defects can be eliminated as creep-controlling species. We have performed creep experiments as a function of temperature at a stress of 244 g per sq mm under conditions which fixed the lead vacancy concentration, V&apos;, at 1016, 3.2 x 1016, and 3.2 x 1017 cm-3, and one were the sulfur vacancy concentration, Vs, was held at lo17 cm-3. The results are presented in Fig. 2 as creep rate, k, vs reciprocal of absolute temperature, 1/T. Specimens 34, 35, and 36 were deformed under constant lead vacancy concentration while specimen

Jan 1, 1969

By W. Jolley

Decarburized iron and Fe-3.28 pct Ni alloys were impact and tension tested in the temperature range of ambient to 4°K. It was found that alloying with nickel improves the fracture properties of the ferrite matrix. The improvement in toughness of iron alloyed with nickel is attributed to the effect of the nickel addition on the temperature and strain rate dependence of the yield stress as well as on slip behavior. The Fe-Ni alloy exhibits wavy slip when strained at temperatures down to at least 50°K. This behavior contrasts with that of the unalloyed iron where a change It is a generally accepted fact that of the common alloying elements of steel only nickel and manganese improve both the room-temperature yield strength and the notch impact properties. It has been argued for a number of years that manganese refines the ferrite grain size, the pearlite spacing, and the grain boundary carbides in medium- and low-carbon steels and thereby increases resistance to brittle fracture.&apos;&apos;&apos; This hypothesis recently was confirmed for a 0.04 pct C iron containing manganese, but at the same time from wavy to planar slip occurs at about 120°K. The observed lower temperature and strain rate dependence of the lower yield stress in the Fe-Ni alloy as compared to the unalloyed iron may be attributed to this difference in slip behavior. In contrast to suggestions published previously, transmission electron microscopy showed that the uniform dislocation distributions and the lack of dislocation tangles which are produced by low-temperature straining of bcc materials cannot be attributed to the absence of cross slip at these temperatures. no increase in notch toughness was observed in a decarburized Fe-Mn alloy.3 It thus appears that manganese only increases the toughness of Fe-Mn-C alloys by refining grain boundary carbides and has no toughening effect in carbon-free iron. On the other hand, the mechanism whereby nickel improves toughness has not been established. Hodge et a1.4 have clearly shown that a 3.28 pct Ni addition lowers the impact transition temperature of 0.02 pct C steel approximately 35°C when the grain size is maintained constant. Recently, Wullaert and Tetelman6 stated that nickel refined the grain boundary carbides of an Fe-C alloy and consequently increased the toughness. They also observed the previously reporteda-&apos;

Jan 1, 1969

By J. E. Neal, C. T. Naber, O&apos

Silicon thin films were deposited by electron beam evaporation in an ultrahigh vacuum onto (0001) and (1102) sapphire substrates. Attempts were made to correlate the structural properties of the deposited silicon films with the following: 1) substrate orientation, 2) substrate surface condition, 3) substrate temperature, and 4) deposition rate. The substrate temperatures were varied between 500° and 1000°C and the deposition rates were varied between approximately 50 and 700A per min. The following sapphire surface treatments were investigated: 1) annealing in the ultrahigh vacuum at 1200° C; 2) heating in a hydrogen atmosphere at about 1350°C; and 3) etching with silicon by evaporating silicon onto sapphire substrates heated to 1200° or 1300°C. Twinned silicon films were occasionally formed at substrate temperatures between the 800° and 1000°C on unprocessed mechanically polished substrates; however, the reproducibility and crystallinity of these films were generally poor. Single-crystal and twinned silicon films were formed at substrate temperatures between 700° and 1000°C on substrates which were silicon-etched at 1300°C prior to deposition. Fiber texture films were formed at substrate temperatures between 500° and 700°C. The (111) lattice plane of the silicon single-crystal films was parallel to the (0001) sapphire plane and the (100) silicon plane was parallel to the (1102) sapphire plane. TECHNIQUES are well-established for growing single-crystal silicon thin films on sapphire by chemical methods.&apos;-* Vacuum epitaxial techniques have a number of advantages over chemical epitaxial techniques in the fabrication of thin film microcircuits.5 One of the most significant is that vacuum techniques are compatible with well-established procedures for forming vacuum-deposited thin-film resistors, capacitors, and interconnections. Salatna, Tucker, and young6 recently reported the formation of relatively poor crystalline-quality silicon films on sapphire by electron beam evaporation in a vacuum of about 7 x 10-7 Torr. The purpose of the investigation described here is to determine the relationships between the structural properties of silicon thin films deposited on sapphire substrates by electron beam evaporation in an ultra-high vacuum and the following: 1) substrate orientation; 2) substrate surface condition; 3) substrate temperature; and 4) deposition rate. The substrate temperatures were varied between 500° and 1000° C and the deposition rates were varied between approximately 50 and 700A per min. Two orientations of sapphire were used: (0001) and (1102). The thick-nesses of the films were between 8000 and 16,000A. The morphology and crystallinity of the deposited films and substrate surfaces were investigated by optical microscopy, electron microscopy, and electron diffraction. APPARATUS AND PROCEDURE A cross section of the ultrahigh-vacuum thin-film evaporator is shown in Fig. 1. The bell jar is stainless steel and copper gaskets are utilized at all seals. High vacuum is attained by a 6001iter per sec ion pump and a titanium sublimation pump. Sorption pumps are used to rough the system to a pressure of about 10 µ prior to starting the ion pump. Vacuums in the 10- 10 Torr range were attained after baking the system at about 250°C for 8 hr. Vacuums in the 10-8 to 10-9 Torr range were maintained during silicon evaporation. The silicon charges, which were cut from p-type single-crystal boules which had resistivities between 2000 and 4500 ohm-cm, were placed in the water-cooled copper crucible of a 180 deg bent-beam 5-kw electron beam evaporator. During evaporation, a molten zone was formed in the top center of the silicon charge, and the portion of the silicon charge in contact with the water-cooled crucible remained solid. The substrate heater, which has been described

Jan 1, 1969

By Heribert Wiedemeier, Ali Khan

The tetnperature-conposition phase diagram of the syste,n MnS-CdS has been investigated over a range fro)n 600° to 1000° C. The small degree of solid solution on the MnS rich slde cornpared to the large CdS rich single-plzase region could be esplained by the difference in strzrctures of the cotnponents and the relative sizes of the metal ions. The change in lattice parameter as a function of cot)zposition is linear atzd jollous Vegavd&apos;s rule within experittzental limits of error. Mns and CdS have gained considerable attention in recent years because of their interesting solid state properties. In order to investigate such properties and thermodynamic quantities of mixed compositions of transition metal chalcogenides, it is necessary to establish their phase diagrams. Two earlier publications are concerned with the MnS-CdS system. Schnaase&apos; found complete miscibility when MnS and CdS were co-precipitated in aqueous solutions at room temperature. However, there is evidence that the mixed crystals were not stable over the entire range of composition. roger&apos;s&apos; investigation of the ternary system ZnS-CdS-MnS at 900" C indicates a solution of 48 mole pct MnS in CdS. During the course of this work which covers a temperature range from 600" to 100O° C, emphasis has been placed on the use of high-purity materials and well-defined modifications of starting products. EXPERIMENTAL Starting Materials. The stable green modification of MnS with NaCl structure was prepared by direct fusion of the elements and by chemical transport reaction. Stoichiometric amounts of manganese of 99.99+ pct purity and of sulfur of 99.999 pct purity from Gallard-Schlesinger Corp. were sealed in an evacuated quartz tube at a pressure of 10"5 mm Hg and annealed for 48 to 60 hr at 800°C. The quartz tubes used throughout this work were outgassed under high vacuum at a temperature of 90OU to 1000° C for 12 to 18 hr. For the synthesis of MnS by chemical transport3 stoichiometric ratios of elemental manganese and sulfur and small amounts of iodine were sealed under vacuum in a quartz tube, which was placed in the temperature gradient, 900/800-C, of a two zone furnace. Single crystals of MnS in form of platelets and octahedra were deposited at the cooler end of the tube. The manganese content was determined by EDTA titratin. A typical result of several analyses was 63.05 pct Mn which agreed well with the computed value, 63.14 pct. Commercially available CdS of 99.9+ pct purity, a mixture of the cubic and hexagonal forms, was converted into the hexagonal high-temperature modification by annealing CdS under vacuum in quartz tubes at 700° C for about 36 hr. As a second method, cadmium sulfide was transported in a temperature gradient, 70O° /650" C, with in vacuo sublimed iodine from the hot to the cooler zone of the tube. Large sized crystals in form of hexagonal columns and some platelets were obtained. An average result of the cadmium analysis by EDTA titration4 was 77.93 pct in good agreement with the computed value, 77.81 pct. Only the NaCl modification of MnS and the wurtzite modification of CdS were used for the solid solutions. Preparation of Solid Solutions. Finely powdered MnS and CdS samples were thoroughly mixed in molar ratios and compressed into pellets of about 6 mm diam and 2 mm in height at a pressure of approximately 13,500 atm.

Jan 1, 1969

By John H. Smith, Michael B. Bever

Pure gold was deformed by wire drawing at room temperature and 78°K. After deformation at room temperature, the stored energy and the resistivity increment reached nearly constant levels at high strains, whereas the yield stress continued to increase with strain. After deformation at 78K, the stored energy, the reszstivity increment, and the yield stress were larger than after deformation at room temperature mzd increased continuously with strain. Annealing at THE stored energy and the changes in properties resulting from cold working of Au-Ag alloys by various processes have been the subject of a series of investigations in this laboratory.&apos;-&apos; The work reported here room temperature after deformation at 78°K did not affect the yield stress appreciably. The stored energy, resistivity increment, and Lncrease in yield stress after deformation at room te-lnperature can be explained primarily in lerrns of dislocations while point defects, as well as dislocations, contribute to the changes in these properties after deformalion at 78°K. extends this research to pure gold. The stored energy, the resistivity increment, and the tensile properties after deformation by wire drawing were measured as functions of the strain at room temperature and at 78°K. The effect of the testing temperature and the effect of intermediate annealing at room temperature before testing at 78°K on the tensile properties of gold deformed at 78°K were also investigated. wire drawing made it possible to use a large range of strains, which was desirable because previous work on the deformation of gold had been carried out mainly at relatively small strains.&apos;-l2 Also, wire specimens

Jan 1, 1969

By Charles C. Boley

The Bureau of Mines dried and carbonized two wood wastes, one softwood (redwood) and one hardwood (oak), using continuous, vertical entrainment techniques previously developed for use with coal. It was demonstrated that these techniques are readily applicable to wood waste and that appreciable changes in the yields of carbonization products can be obtained by varying operating conditions. A limited amount of experimental work was done on briquetting the char-coals. Firm briquets were formed with oak charcoal, although greater quantities of starch binder than used commercially for kiln-produced charcoal were required. Redwood charcoal did not briquet successfully under the test conditions employed.

Jan 1, 1969

By S. E. Khalafalla

The Bureau of Mines investigated the metallothermic reduction of copper oxide as a function of temperature, reactant proportions, form of reductant, and gaseous environment, using iron and steel scrap reductants. The reaction proceeded rapidly with powdered iron at temperatures above 560° C, attaining over 95 percent copper metallization within 3 hours. The importance of inter-reactant contacts on the extent of the reaction was evident from the variable, but usually lesser, degree of metallization obtained with iron from tin cans and automobile steel scrap. Reduction decreased as the molar ratio of copper to iron increased between 1 and 3. The most favorable gaseous environment for the reaction was a static helium atmosphere containing about 0.6 percent water vapor. Ferrothermic extraction of copper from its oxides appears to be essentially a "solid-state cementation" process. While ordinary cementation processes must be preceded by leaching, the ferrothermic method avoids this generally slow step and also the water pollution caused by the leaching agents. Sulfidic copper concentrates could likewise be reduced with metallic iron following their complete oxidative roasting.

Jan 1, 1969

By D. Atkinson, C. Bodsworth, I. M. Davidson

A geometric model of interstitial solid solutions, which has been used previously as a basis for the prediction of carbon activities in Fe-C austenite, is shown to serve also for the calculation of nitrogen activities in Fe-N austenite. The model has been developed to enable predictions to be made of the activities of an interstitial element in the presence of two host atom species. The activities calculated via the model are shown to be in satisfactory agreement with the measured values in the austenite phase for carbon in Fe-C-Co, Fe-C-Cr, Fe-C-Ni, Fe-C-~n, Fe-C-Si, and Fe-C-V alloys and for nitrogen in Fe-N-Ni alloys. The effect of the second substitu-tional solute on the logarithm of the activity of the interstitial element is expressed as the product of a constant mad the atomic concentration of that solute. The constants so derived we related to the thermo-dynamic interaction coefficients which describe the effect on the activity coefficient of carbon of an added solute element. In recent years the thermodynamic activities of carbon and nitrogen in the single-phase austenite field have been determined for iron binary alloys and for several iron-base ternary alloys. In order to extend the use of these measurements, it is desirable to be able to predict with reasonable accuracy the activities of the interstitials at compositions and temperatures other than those which have been measured experimentally. In all the systems studied to date, the interstitial elements do not conform to ideal behavior. Hence, the available data cannot be extrapolated or interpolated using the simple thermodynamic concepts of solutions. Several models have, therefore, been formulated for the purpose of predicting the activity of an interstitial element in the presence of one species of host atom. These models can be divided into the geometric1"5 and energetic6-&apos; types. The former group is based on the assumption that at low concentrations the activity of the interstitial species is determined by a composition-dependent configurational entropy term and an excess free-energy term which is temperature-dependent but independent of composition. The purpose of this paper is to show that the treatment, based on a geometric model, can be extended to enable predictions to be made of interstitial activities in the presence of two substitutional host atom species. THE CONFIGURATIONAL ENTROPY OF MIXING ICaufman5 has shown that the configurational entropy, S,, for a binary solution comprising of a host atom species, A, and an interstitial species, I, can be expressed as: where NI is the atom fraction of the interstitial species, R is the gas constant, and (2 - 1) is the number of interstitial sites excluded from occupancy by the strain field around each added interstitial atom. The number of interstitial sites per host atom, p, is unityg for the fcc austenite solutions considered here. The configurational entropy of mixing for a ternary solution comprising two substitutional atom species, A and B, and one interstitial species, I, can be derived similarly. Let the number of atoms per mole of each of these species in the solution be represented by «a, ng, and nI. From geometric considerations, it is improbable that the addition of a few atom percent of a second host atom species will change the type of sites (i.e., octahedral) in which the interstitial atom can be accommodated in the austenite lattice. At higher concentrations (determined largely by the relative atomic radii of the atomic species present and any tendency to nonrandom occupancy of the host lattice sites) other types of interstitial sites may become energetically favorable. Restricting consideration to compositions below this limit, for 1 = 1 the number of suitable interstitial sites is given by (n + nB). However, if each interstitial atom excludes from occupancy (Z - 1) additional sites, the total number of sites available for occupation is reduced to (n + ng)/Z. The number of vacant interstitial sites is given by: The total number of recognizable permutations of the atoms must include the recognizable, different configurations of the A and B atoms on the host lattice. Assuming that these arrangements are purely random, and are not affected by the presence of the interstitial species, the total number of recognizable permutations in the ternary alloy is given by: The configurational entropy is obtained by expanding, using Stirling&apos;s approximation, and collecting like items, as:

Jan 1, 1969

By A. T. Yu

The broken hill proprietary company Ltd., Australia&apos;s only steel producer, has come a long way. Since 1885 to reach today&apos;s. Capacity of 6.6 million long tons of ingot steel per year.* its Newcastle steel complex in New South Wales, located 100 miles north of Sydney and on-stream since 1915, has likewise shown continued impressive growth (fig. 1). The most recent expansion plans at Newcastle call for sub¬stantially increasing its production, with the help of some added facilities, but principally relying on the increase in efficiency of the furnace operation. Its modern raw materials blending system will playa major role in meeting Newcastle&apos;s new targets.

Jan 1, 1969

Laboratory electrical resistivity measurements of rocks are reviewed. Inductive and galvanic methods are discussed together with the ten important experimental factors which should be considered in an investigation.These experimental factors are electrodes, sample preparation, measurement errors, temporal current variations, current density, frequency, electrolyte composition, electrolyte saturation, pressure, and temperature.

Jan 1, 1969

By S. V. Krusiewski, J. W. Gabelman

Regional metallogenic zones and areas of equal paragenetic range have been interpreted from a compiled metallogenic map. of Mexico. Mineralization gradients of the pattern subsequently identified extend inland from coastal zones of high-temperature mineralization, and join in a central longitudinal zone of relatively low-temperature mineralization, apparently leaving no zonal room for lowest temperature deposits. The striking regional zoning pattern can be correlated with regional deformation gradients of similar position and orientation. The gradients represent at least three major orogenic cycles in two structural belts. Paleozoic structural belts existed along each coast with deformation gradients diminishing inland toward a narrow, central peninsular craton. The Mesozoic-Tertiary Mexican (Cordilleran) belt covered the entire country with a gradient oriented toward the Gulf of Mexico. Most ore deposits in this belt are of Tertiary age, although Tertiary mineralization gradients seem to have "inherited" the pattern left by Paleozoic tectonic gradients. Mineralization gradients can be used to identify the regions most favorable for the occurrence of selected metals. A metallogenic province is characterized by particular proportions of various metals, and the relative proportions can vary from province to province; but within any province the same intensity of mineralization would produce similar deposits in different places. Declining intensity of minetalization produces different kinds and sizes of deposits in zones that are concentrically arranged around sites of strongest rock alteration. On a regional basis, districts of similar average intensity of mineralization occur in zones that generally parallel some tectonic grain with the result that tectonic deformation has been designated a principal cause of mineralization. Variations in the type and intensity of deformation would determine the type as well as size of metal deposits. Mexico is especially favorable for such a study be- cause of its great abundance and variety of epi-genetic mineral deposits in various lithologic, structural and tectonic environments. The concept is also useful in recognizing portions of Mexico favorable for the occurrence of specific metals. METALLOTECTONIC ZONING IN MEXICO Theory: In studies of individual districts and groups of districts throughout North and South America, areal zoning of metal deposits generally seemed to respond to the paragenetic sequence of iron, gold, copper, zinc, lead, silver, antimony and arsenic, gold and fluorite. However, the definition of district zones is greatly obscured by contemporaneous or rhythmic deposition of metals, especially in the middle of the paragenetic range, and by the common superimposi-tions of different generations of metals. Zones could usually be distinguished only for groups of metals, such as early precious metals, base-metal sulfides, sulfosalts and late precious metals. The best defined zoning in a district is normally the spatial separation of the greatest volumes of altered and metallized rocks.&apos; Exceptions are districts representing the high- and low-temperature extremes of the mineralization range where the former creates a matrix for the latter. In most districts the total quantity of alteration products is greatly in excess of, and appears to be roughly proportional to, the total quantity of metallization products. Subsequent to the bicomponent nature of each district, the most important mineralogical feature is the great excess of one to several metals or minerals which results in a district identifiable as one of predominantly gold, copper, lead-zinc, fluorite, etc., although a great variety of other elements may be present. The para-genetic range for the abundant elements in any district is only a portion of the entire possible range for all the elements representing the complete process throughout the region. Early during investigations of this type, it became apparent that the consistent bicomponent character of districts allows two methods for studying epi-genetic mineralization patterns. One is to identify and plot altered rock "pipes,"* which are easily recognizable in the landscape by their anomalous

Jan 1, 1969

By J. Campbell

Various models are discussed for the evaluation of the negative pressures which may occur in solidifying materials which exhibit various deformation modes: elastic-plastic, Bingham, viscous, or creep flow. The inadequacy of the previously proposed elastic-plastic solution for solidifying metals is revealed by comparison with the more reliable creep results which are given graphically for aluminum, copper, nickel, and iron. The maximum tensions experienced in the liquid phase of solidifying spheres ranging in size from large castings to submicron powders are in the range from —10&apos; to —105 atm for these metals. THERE has been much recent interest in the negative pressures associated with the volume change on solidification and in the possibility of the occurrence of cavitation. Considering the freezing of a highly supercooled liquid, an attempt to evaluate the stresses in the liquid ahead of the rapidly moving solidification front has been made by Horvay1 on a microscale and by Glicksman2 on a macroscale. In a casting of a wide freezing range alloy, the pressure differential due to viscous flow of residual liquid through the pasty zone has been discussed by Piwonka and Flemings,3 In a previous publication4 the author has attempted to estimate the negative pressure occurring in the residual liquid of a spherical casting, employing an elastic-plastic model to describe the collapse of the solidified shell under the internal tension. An earlier model assuming a rigid shell was shown to be inaccurate by many orders of magnitude. The elastic-plastic model is critically reviewed here, and other models are developed which are thought to be more closely related to metals and other materials near their melting points. The spherical geometry (Fig. 1) is chosen because the highest shrinkage pressures would be developed, although the analyses are readily adaptable to cylindrical geometry. A parallel sided casting experiences little internal tension because of the relatively easy dishing inward of the sides. (This commonly observed phenomenon has previously been attributed solely to atmospheric pressure.) Furthermore, small regions of confined liquid in a large solidified volume of a casting approximate reasonably well to spherical geometry. ELASTIC-PLASTIC MODEL The author has shown4 that as solidification proceeds the internal hydrostatic tension builds up until the elastic limit of the shell is exceeded. At this point the internal pressure is closely -2Y/3. Subsequently a plastic zone spreads from the inner surface toward the outer surface of the shell. When the whole casting is deforming plastically a rather more generalized analysis taking account of the externally applied pressure PA + 2y/b gives the internal pressure as: P = Pa + 2y/a + 2ys/b - 2 Y In(b/a) [1] The 2y/a and 2ys/b terms result from the tendency of the liquid-solid and solid-vapor interfaces to shrink, reducing their energy, and thereby helping to collapse the solid phase and compress the liquid phase. The 2y/b term would be important only for powders. The last term arises because of the plastic restraint of the solid, resisting collapse and so effectively expanding the residual liquid. From Eq. [I] it is easily shown that there is a minimum in the pressure at the radius amia= y/Y [2] which is of the order of 103K for the metals aluminum, copper, and iron, and corresponds to the minimum pressure Pmin = 2 Y[l-ln(bY/y [3] The results of a fully worked out elastic-plastic solution are given in a previous reporL4 The main criticism which may be leveled at this analysis when applied to metals at their melting points is the strong dependence of the yield stress on the strain rate. The strain rate varies with both solidification conditions (e.g., whether chill-cast or slowly cooled) and during solidification, as is indicated in the following section. Thus an appropriate choice of Y is very arbitrary. Before proceeding to a discussion of models which are strain-rate-dependent, it is necessary to evaluate the strain rate as a function of the rate of solidification. SOLIDIFICATION RATE Various empirical relations have been deduced5 for the rate of thickening of the solid shell by pour- out tests on partially solidified spheres. These, however, are unsatisfactory for our purposes since they become very inaccurate when the liquid core is very small. A theoretical approach is therefore necessary, and some solutions are set out below. Making the assumptions of constant surface temperature of the casting during freezing, no superheat, and a material freezing at a single temperature, Adams8 deduces the approximate solution: which becomes when b » a: Employing a semiempirical approach vallet6 finds:

Jan 1, 1969