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By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The 'system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and 'p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By J. G. Y. Chow, S. B. McRickard

The tensi1e properties of Ferrovac iron have been studied from 4° to 300°K. The stress required for macroscopic yielding was found to he constant below approximately 50°K. The effect of mechanical twinning on this low -temperature stress plateau was investigated. The onset of twinning occurs in this iron between 130° and 150°K and depending on its previous thermal history the twinning-stress curue may drop below or remain above the vield-stress curves as the temperature is lowered. Twinning has been shown to initiate slip in quenclzed iron at low temperatures. In no instances, however, did the onset of twinning alter the continuity of the yield stress -tempwature curve. Our data shows that carbon inhibits twinning and slip at low tem-peratures. This observation nay be used to explain the ductile-to-brittle transition in iron. The effect of fast neutron irradiation on yielding and embrittlement in iron and Fe-C alloys is offered as supporting evidence for this viewpoint. THE mode of yielding in iron at low temperatures was studied in an attempt to find an expression based on a single mechanism to describe the thermal dependence of the yield stress of iron. There are two types of inflections observed in the variation of the yield stress with temperature in iron and Fe-C alloys. The first is associated with ductile behavior and consists of a region extending 50" to 100°K above absolute zero in which the yield stress is independent of temperature. The second is observed in more brittle materials such as Fe-C alloys and irradiated iron and consists of an abrupt discontinuity in the yield curve as the temperature is lowered through a ductile-to-brittle transition point. The temperature dependence of the yield stress for iron with four grain diameters as found in this study is shown in Fig. 1. To varying degrees all the curves appear to flatten or approach an asymptotic value as the temperature is lowered below 50°K. Several other investigators1,2 have observed a plateau in the yield stress of iron and steel at low temperatures and in 1956 Louat3 presented a theory which contained an explanation for this behavior. In a subsequent exchange with Erickson and Low4'5 who attributed the plateau to the onset of mechanical twinning Louat8 showed that twinning first occurs in iron and steel tested in tension at temperatures as high as 140°K which is well above the observed plateau in yield stress. Furthermore he pointed out that both twinning and slip are basically dislocation processes and that with modified parameters his original theory still applied when deformation is initiated by twinning. Variables which affect the ductile-to-brittle transition in iron are test temperature, strain rate, composition and grain size.7 LOW,8 Hahn et al.,9 and Hull10 have provided evidence which links brittle fracture at a given temperature with the specimen grain size and the onset of twinning. In fact, Hull equates the brittle fracture stress to the twinning stress. On the other hand brittle fracture has been observed in the absence of twinning and priestnerl1 has given a fracture criterion which is valid whether or not fracture is preceded by extensive twinning. The data presented here clarify the role of twinning in the low-temperature deformation of iron. Strong evidence is given that the amount and distribution of interstitial impurities such as carbon are of

Jan 1, 1965

By Eric R. Jette

In order to control a chemical process by other than empirical, rule of thumb methods, two types of knowledge concerning the reactions involved must be available: (1) the thermodynamics of the reactions, and (2), by no means less important for efficient operation, the mechanisms and kinetics of the reactions. Information on the thermodynamic side enables the operator to decide upon initial and final conditions, whether heat must be added or removed from the system, whether the reactions proceed farthest in the desired direction at high pressure or low, etc. Knowledge of the mechanisms involves the determination of the individual steps by which an initial set of reactants, under given conditions, proceed to give the desired final products and kinetic studies upon which the mechanisms are based give the speed at which each of these reactions or steps take place. Thus thermodynamic studies of a reaction enable the operator to control the direction and extent to which the reaction can proceed, while kinetic studies enable him to control rates and thus the time efficiency of the operations. The thermodynamics set the limit to which the reacting system approaches; the kinetics tell how fast the system actually approaches this limit. The two types of information are complementary and not antagonistic even though in discussing the mechanism the introduction of thermodynamics is entirely needless and generally of no assistance, while in thermodynamic studies mechanism need not even be mentioned. Heterogeneous Reactions The thermodynamic side of metallurgical reactions has received much attention in the past; the mechanisms, relatively, very little. The main reason for our present lack of information on the mechanisms of these reactions lies in the fact that every one of importance is a heterogenkous reaction; i. e., the substances involved in the reaction exist in more than one phase, while, if we neglect the large amount of work which has been

Jan 1, 1931

By E. Buehler, R. H. Willens

A Hew melting technique has hem adapted to the rapid quenching of- alloys from the liquid state. The inelting method has no limitations on the alloys investigated for there is no reaction with crucible materials and the most refractory materials are easily melted. The vate of heating is so rapid that alloys which have a high vapor pressure constituent can be melted with a minimal loss in material. Several new superconductovs have been discoveved by vapid quenching of lolten alloys. THE rapid quenching of alloys from the liquid state has led to the discovery of many new metastable phases. The methods initially used were limited to alloys which did not react with crucible materials.1,2 There was also the unmentioned limitation in tem- perature. Alloys with melting points much greater than 2000°C could not be melted in the rapid-quench apparatus. Recently, there have been successful attempts to rapidly quench reactive alloys by Moss et at. and Matthias Moss et al. injected powdered material (325 mesh) into a high-temperature plasma and the high-velocity molten droplets impinged on a cooled copper plate. The technique innovated by Matthias was to melt the alloy in an arc furnace and splatter it against a copper plate by means of a high-velocity gas jet aimed at the melt. I) FAST COOLING APPARATUS The creation of a metastable phase in a given alloy system by rapid cooling from the melt is contingent on the quenching rate. Some alloys require very slow rates while other alloys require the ultimate in quenching rate. At the present time, the vertical-gun technique of Duwez and willens' has demonstrated, in practice, the highest quenching rates and thus the best

Jan 1, 1967

By I. Fatt, D. N. Saraf

A method is described for measuring two- and three-phase relative permeabilities in sandstones or sand packs using a nuclear magnetic resonance (NMR) technique to determine fluid saturations. Two- and three-phase relative permeabilities have been determined on Boise sandstone using the NMR technique of saturation measurement. Three-phase relative permeability to water was found to depend only on the water saturation, whereas three-phase permeability to oil depended on both the water and oil saturations. Relative permeability to gas in three-phase flow was found to depend only on the total liquid saturation. INTRODUCTION Three-phase relative permeabilities are extremely useful in calculating field performance for reservoirs being produced by simultaneous water and gas drives. Three-phase relative permeability data are also needed for analyzing solution gas-drive reservoirs which are partially depleted and are being produced by water drive. Some thermal recovery processes involve three-phase flow which require three-phase relative permeability data for predicting reservoir behavior. Unfortunately, three-phase relative permeability measurements have rarely been made. Also, because of the scarcity of three-phase data, it has not been possible to date to relate other measured rock characteristics to the relative permeabilities with a great certainty. Leverett and Lewis,l Reid2 and Snell3 have reported three-phase relative permeability data on unconsolidated sands. Leverett and Lewis used ring electrodes spaced along the length of the sand sample to measure the resistivity of the sample which was assumed to be monotonically related to brine saturation. Gas saturation was determined from pressure-volume measurements. Oil saturation was obtained by material balance on the cell containing the sand sample. This method is involved and time consuming. Another difficulty arises from the fact that the resistivity of the sand is a function not only of saturation of brine but also of the distribution and saturation history of the brine in the pore spaces. Reid2 used a gamma ray absorption technique for measuring liquid saturation. This method has the disadvantage that total liquid saturation rather than oil or brine saturation is all that can be measured and still another method is required to determine the saturations of individual components. snel13 used a neutron bombardment method which also required a separate determination of the individual component saturations. Caudle et al.4 measured three-phase relative permeability on consolidated sandstones using vacuum distillation for determining fluid saturations. Distillation after each reading makes this technique very lengthy and time consuming. Corey et a1. 5 and Naar and Wygal 6 measured three-phase relative permeability on sandstones by the capillary-pressure method. Semipermeable diaphragm assemblies were used at each end of the core specimen to keep the water phase in the core. Gravimetric methods were used to determine fluid saturations. Sarem7 recently reported an unsteady-state method for measuring three-phase relative permeability on sandstones. This method is an extension of Welge's method8 for measuring two-phase relative permeability. Although Sarem's method is simple and comparatively fast, the assumptions involved may oversimplify the problem. Sarem's assumption, that in all rocks relative permeability to each fluid will depend only on the saturation of that fluid, seems to be rather unrealistic. Neglecting capillary effects at the end of the core is also a weak assumption. Donaldson and dean9 measured three-phase relative permeability using a method similar to Sarem's.

By G. B. Pryde

IN laying out a new mine, provision should be made for the ultimate recovery of as much coal in any given bed as is consistent with safety and economic mining. Though each mining district, if not each individual mine, has problems that make the adoption of any hard and fast rule impossible, certain basic principles are adapted to practically all conditions. One of the most vital is the provision for barrier pillars of ample dimensions to protect all haulage and permanent airways during the life of the property. Where conditions permit, room or butt entries should be driven on the strike or slightly to the raise and rooms turned at right angles to said entries. The width of rooms and room pillars is governed by conditions prevailing in the mines under consideration. A safe rule is: In advancing, extract not more than 25 to 35 per cent. of the entire seam; in exceptionally thick seams, considerably less than 25 per cent. should be taken. Rooms usually vary in length from 250 to 350 ft. (76 to 106 m.) with a barrier pillar of not less than 80 ft. between the last crosscut in rooms, and entry and room crosscuts should be driven on sights; room crosscuts should be driven at right angles to the direction of the rooms. In mines under excessively heavy cover or where roof conditions are bad, rooms should be driven narrow and a barrier pillar left at every fifth to tenth room. This barrier should be of such dimensions that one or more rooms, with pillars of usual dimensions, may be turned through it when the barrier is no longer required. Two of the advantages of such a barrier are the protection of the panel against peaking of roof load during pillar extraction and the easy closing of the entry in case of fire.

Jan 2, 1921

By H. A. Wriedt

At 500°C (932°F) the range of y' iron nitride is from 5. 77 + 0.03 wt pct N (in coexistence with a iron) to 5.88 * 0.03 wt pct N (in coexistence with E iron nitride). Stoichiometric "Fe,N" (5.900 wt pct N) is near the upper extreme of possible compositiom. The depe-dence of nitrogen activity (expressed as pnh,/Ph,) on nitrogen content is described satisfactorily by a "Langmuir" isotherm: At even the highest nitrogen concentrations, less than 0.18 pct of' the nitrogen atoms present are impositions of disorder. Past investigations1-4 of the Fe-N system have left only details of the thermodynamic behavior of the y' nitride, "Fe,N9', to be studied. The present investigation was made to establish more precisely than hitherto the limits of composition and the relation between composition and nitrogen activity at 500°C. EXPERIMENTAL TECHNIQUE The compositions of nitrides in equilibrium with various NH, + Hz mixtures at 500°C were determined from the weights gained by 0.02-in.-thick (4.0 to 4.5 g) strips of purified iron* when the nitrides were formed A description of the gas generation and furnace system has been published.5 Cracking and blistering during conversion of the original solid iron at 550°C injected considerable porosity into the strips without causing their disintegration. The time for complete conversion was significantly lowered by periodically reducing partly nitrided specimens in hydrogen and then reexposing them to the nitriding gas. Gas mixtures producing single-phase were used in the equilibrations at 500°C. Equilibrium was regarded as existing when the specimen weight was not detect-ably affected by further exposure to the same conditions. The gas compositions and nitrogen activities at which y' transformed to a iron (lower activity limit) and to E iron nitride (upper activity limit) were redetermined during the investigation. A specimen was equilibrated in an NH, + Hz mixture at 500°C and then exposed to a s1ightly different gas. When equi- librium had been reestablished the gas was again changed slightly. At each stage of this repeated process, while the specimen was reacting with the gas, the variation of its weight with time was observed. The onset of phase transition was marked by an abrupt change in the amount and rate of weight gain or loss. The specimens were weighed outside the furnace, in air and at room temperature, on a balance with 0.05 mg precision. When it was found that the specimens were oxidizing at a significant rate during the weighing, a series of timed weighings was made with each specimen, starting 1 min after its exposure to air. RESULTS AND ANALYSIS The gain in specimen weight from oxidation during weighing was linear in the logarithm of time between 1 min and about 2 hr, Fig. 1, later becoming linear in the cube root of time. In the logarithmic period, nitride specimens oxidized two to three times as fast as

Jan 1, 1970

By Peter Soo

Pvestrained Ferrovac E iron has been neutron-irradiated at approximately 90°C to an integrated flux of 1020 nut (E > 0.82 mev]. The irradiation was found to produce an incveased temperature dependence of the flow stress in addition to a greatly increased athemal stress. Measurements of the flow stress and stress relaxation, from which the activation volume and activation energy for slip were deduced, show that neutron irradiation changes the rate -controlling slip process to one based on dislocation interactions with tetragonal distortions which are Produced around submicroscopic interstitial loops in the lattice. The study indicates that without prestraining prior to irradiation the chances of detecting a change in the rate -controlling slip process are greatly reduced because in the initial stages of slip a substantial fraction of the radiation defects are swept out of the slip plane by gliding dislocations. Thus, activation parameters which are subsequently measured are representative of a greatly reduced defect density and would not differ appreciably from those for unirradi-ated material. The large increase in the athermal component of the flow stress is probably connected with the presence of depleted zones in the lattice which are introduced by irradiation. ALTHOUGH fast neutron-irradiation has not been observed to markedly alter the activation parameters for slip in bcc metals,' small but significant changes do occur. Most experimenters agree that irradiation predominantly increases the athermal component of the yield stress.'-= In addition to this, Laidler and smidt7 have shown that in iron irradiated to 5 X 10" nvt and molybdenum irradiated to 10" nvt, changes occur in the activation volumes for slip. A similar conclusion has been reached by Milasin and Malkin8 for irradiated iron. Work by Ohr et a1.5 shows that for Ferrovac E iron, irradiated to 1.2 X 1016 nvt, small increases in the activation energy for slip also occur. So far these changes in the activation parameters have not been explained on a firm theoretical basis. One important factor which would minimize the chances of detecting a change in the slip mechanism upon irradiation is the presence of "channeling" which has been observed in molybdenum,9 niobium,10 and iron.11These channels are formed by gliding dislocations which sweep irradiation defects out of the active slip planes and thereby create zones in which continued dislocation motion is encouraged. The activation parameters for the dislocations gliding in the defect-free channels would, therefore, be similar to those for unirradiated iron and a change in the rate-controlling slip process would be difficult to detect. In the present work, an attempt has been made to reduce the effect of uneven deformation on the measured activation parameters for slip in neutron-irradiated Ferrovac E iron polycrystals, so that a more realistic assessment of the effects of neutron-irradiation could be made. Primarily, the experiments involve the irradiation of specimens which had been prestrained to 9 pct elongation at room temperature prior to insertion into the reactor. It was hoped that the introduction of a large number of evenly distributed dislocations would substantially decrease any channeling effect which might otherwise occur. MATERIAL AND EXPERIMENTAL PROCEDURE The starting material was vacuum-melted Ferrovac E iron, an analysis of which is given in Table I. The standard tensile specimen had a gage length of 1.125 in., a cross-sectional diameter of 0.120 in., and a re-crystallized grain size of 1.2 x 10-3 in. All tensile tests were conducted on a floor model "Instron" tensile machine at a strain rate of 3 x 10-4 per sec. The irradiation of the prestrained specimens was performed in the Brookhaven High Flux Beam Reactor to an integrated flux of 1020 nvt (E > 0.82 mev) at a temperature of about 90°C. All specimens were excap-sulated in high-purity aluminum sheaths which were lightly swaged around the samples to ensure good thermal contact. Subsequent measurements on the irradiated specimens showed that within experimental accuracy the swaging had not deformed them. EXPERIMENTAL RESULTS Fig. 1 shows the flow stresses for a series of unirradiated control samples. In order to produce a comparable dislocation substructure throughout the test sm range, all specimens were prestrained

Jan 1, 1970

By Michel Dupuy, Daniel Calais

The study of self-diffusion of plutonium in E phase has been carried out by the welded couples method. The tracer used was puZ4O which is detected by its X-ray emission (conversion lines of uranium which are computed between 13 and 21 kev). Intensities were measured with a scintillation counter. Each layer was removed in a direction parallel to the original interface with a grinding machine and a thickness measured with a pneumatic comparator. The concentration-penetration curves obtained were corrected for the effect of heating time from room temperature to annealing temperature and for the expansion due to phase transformations of plutonium. They were analyzed by the generalized Gruzin method. Self-diffusion of plutonium in E Phase is very fast cm per sec between 500" and 620°C) and the diffusion zones are 2 to 3 mm wide for annealing times ranging from 30 min up to 10 hr. The Arrhenius law gives the temperature dependence in the form: From the point of view of self-dqfusion, PUE phase falls into the anomalous bcc metals category (Tip , Hfp, Zrp, Uy) with a low-frequency factor and an activation energy lower than those provided by standard correlations. No theory proposed hitherto to explain these anomalies (influence of dislocations, of extrinsic vacancies bonded to inlpurities, of bi-vacancies) can clearly explain the self-diffusion coeffzcients of plutonium. DIFFUSION in bcc metals is a present-day problem. A recent symposium (Gatlinburg, 1964), followed by a book,' has been devoted to it. A great many experiments seem to show that diffusion in certain bcc metals obeys unexpected laws. The activation energies measured are sometimes strangely low (B hafnium, y uranium). For certain metals (0 zirconium, p titanium) the curves of log D (D = diffusion coefficient) as a function of 1/T (T = absolute temperature) are not linear. The frequency factors Do, which are of the order of 1 sq cm sec-' in fcc metals, vary from 1 to 10~6 sq cm sec-'. Various theories have been put forward to explain these anomalies; none is yet satisfactory. We wished to introduce a new experimental result by studying the self-diffusion in c plutonium. This allotropic phase, stable from 475°C up to the melting point (640°C), is in fact bcc. Unfortunately, nothing is known of the characteristics of the point defects in this phase, which limits the scope of the hypothesis which can be made about the mechanism(s) of self-diffusion in plutonium. 1) EXPERIMENTAL METHODS 1) Principle. We used the welded couple method. The two pellets of the couple initially have different 240 isotope contents (X emitter). After diffusion, the concentration/penetration curves are drawn up by the generalized Gruzin method. 2) Gamma Spectrography. The metal used in our study is plutonium, either low in puZ4O (isotopic content 1 pct) or high in puZ4O (8 pct). The latter also contains plutonium 241 (-1 pct) and 300 ppm of ameri-cium produced by the reaction Pu2U-AmM1 + 8-. The emission spectra of these two plutoniums placed in leak-tight vinyl bags have been studied by y spectrograph~. The detector is a thin crystal of thallium-doped sodium iodide. The activity of the plutonium rich in 240 is about twice that of the plutonium low in 240 in the energy band of 17 kev (L conversion lines of uranium); this band was used in these measurements. 3) Preparation and Examination of the Diffusion Couples. Diffusion couples were made from plutonium with a high and low PU"' content. Pellets (6 6 mm. thickness 3 mm) mounted on a polishing disc with ground parallel faces were polished mechanically on both sides. In this way, pellets with two parallel faces were easily obtained. The polished pellets were joined by a 6 phase anneal (420°C, 1 hr) in a small screw press (pressure of 20 kg per sq mm cold); a centering ring enabled the two pellets to be pressed coaxially. The couples then were subjected to the diffusion treatment by annealing in the E phase in sealed silica ampules in argon at atmospheric pressure. The annealing temperatures and times are given in Table I. The couples were encased in a mild steel ring, the joint interface being thus parallel to the ground face of the ring. The diffusion couple/ring assembly underwent successive abrasions by means of a magnetic plate grinder. The thickness of the abraded layer was measured with a Solex pneumatic comparator when it was less than 0.1 mm (accuracy 0.2 p) or with a mechanical micrometer (accuracy 3 p) for passes of the order of 0.2 mm. All these operations were done in glove boxes, as plutonium is particularly toxic. After each abrasion we determined the emission spectrum of the ground face. The emissive surface is defined by means of a diaphragm 3 mm in diam. We noted more particularly the X activity in the 17-kev

Jan 1, 1969

By O. J. C. Runnalls, L. M. Pidgeon

Some observations on the kinetics of the iodide process are reported. The deposition rate is geometry-sensitive in a system containing a finely divided titanium charge. Further, results indicate that the iodine diffusion rate influences the velocity of the process. The nonvolatile iodide, Til,, forms in the hot filament zone, thus removing iodine from the cycle. TITANIUM metal of 99.9 pct purity may be prepared using a refining technique originated by Van Arkel and de Boer.' The purity of this metal, commonly called iodide titanium, exceeds that produced by any known process. In a recent application, the method was employed by Gonser et al.² to prepare titanium rods up to 2 to 3 cm in diam. In the Van Arkel-de Boer system, the relative influence of the fundamental mechanisms: l—production of titanium iodides, 2—gaseous countercurrent diffusion, and 3—decomposition, on the deposition rate have not been clearly established. Blocher and Campbell" have indicated that the controlling step in the process under practical conditions of operation may be the reaction rate of iodine with the crude metal. Fast' reported that crude titanium metal reacted with iodine rapidly, even at room temperature, in his apparatus. Little has been reported on the effect of gaseous diffusion or decomposition on the deposition rate. It is these aspects of the process about which this investigation is centered. An attempt has been made to separate these latter effects from those due to the formation of the iodides at the crude metal surface by a division of the experimental program. Reaction of Iodine with Titanium Apparatus: In the investigation of gas-metal reactions of this type, the chemical reactivity of the halogen and halide vapors dictates the use of all-glass apparatus. In such a system standard techniques for measuring reaction rates are difficult to employ. Here, a simple apparatus was devised (Fig. 1) so that some indication of the reactivity of titanium powder with iodine vapor could be obtained. A stream of iodine gas was evolved from a bulb of controlled temperature and passed over a sample of titanium powder heated in a horizontal tube furnace. The product of the reaction, TiI4, volatilized and was condensed outside the furnace in a series of four glass bulbs, each cooled to room temperature in turn. Preliminary experiments indicated that distillation was retarded in a sealed evacuated system due to a pressure build-up in the condensing end of the apparatus. Hence, the system was pumped continuously using a mechanical pump and two oil diffusion pumps in series, through a liquid air trap. The iodine bulb was made large and a capillary restriction was inserted between the titanium bulb and the condensers so that the iodine pressure over the metal would approach the equilibrium pressure over solid iodine crystals. The effect of this restriction on the evaporation rate of TiI4, was determined separately. The iodine bulb was heated in an oil bath controlled to ±2°C. The titanium bulb temperature was automatically controlled to ±5°C. Procedure: About 200 mg of —30 mesh titanium powder, weighed to 0.1 mg, was placed in the reaction bulb after part B had been joined to part A. The powder was tapped into a long (5 cm) shallow mass along the bottom of the tube. Two chromel-alumel thermocouples were inserted into the magnesium radiator which was clamped to the reaction

Jan 1, 1953

By R. P. Dolan, W. M. Shedd, B. L. Buchanan

Analytical expressions are derived from empirical data relating the basic physical device parameters to the radiation dose. To put in perspective and justify the approach taken, the overall problem and methods of attempted solution of radiation damage to transistors in a missile or satellite environment is briefly examined. The main emphasis is on a new criteria for neutron radiation hardness and the device design implications resulting from using this criteria. Contrary to other derived criteria, the derived bipolar hardness relation depends mainly on the initial lifetime rather than the base transit time. It is shown, that contrary to previously accepted beliefs, the inherent attainable radiation tolerance of JFET's is at least a factor of ten greater than the radiation tolerance ofbipolars. Experimental results on JFET's designed for maximum neutron radiation tolerance are presented. The accuracy, utility, and range of possible validity of various published lifetime and carrier removal damage constants are discussed. It is well known that transistors are subject to damage due to radiation at much lower radiation levels than those which would cause structural damage to a missile or satellite. The three principal categories of radiation damage to transistors are displacement, ionization, and thermomechanical. The main cause of displacement damage is fast neutrons, and the main effects which permanently degrade transistor operation are minority carrier lifetime reduction and carrier removal. A second-order effect is mobility reduction. The main cause of ionization damage is gamma radiation which results in permanent effects due to charge build-up in the oxide and transient effects due to photo-current generation. The transient effects are usually handled by using circumvention techniques in the electronics system. The extent of the transistor degradation due to displacement and ionization damage depends strongly on the transistor type, whereas the extent of thermomechanical damage does not depend on the transistor type, but depends mainly on packaging and metallization which are common to all transistor types. The standard transistor types are categorized in Fig. 1 and typical cross-sections are shown in Fig. 2. The original reason for the designation of the two classes of transistors was that the unipolar operation depends on only one carrier (majority) and the bipolar operation depends on both minority and majority car- riers. The bipolar is then seriously degraded by minority carrier lifetime reduction, whereas the unipolar or field effect transistor is not. One of the two principle classes of field effect transistors, the junction field effect transistor (JFET), depends strongly on carrier removal. However, the insulated gate (MIS) is little affected by either carrier removal or lifetime changes, but is virtually eliminated as a radiation resistant device because of permanent charge build-up in the insulator caused by ionizing radiation. The bipolar and JFET suffer only minor effects due to charge build-up in the oxide passivation when compared1 to the MOS. This is because the active region of the MOS is adjacent to or part of the oxide layer. It is then the bipolar and JFET which are potentially resistant to permanent radiation damage. DERIVATION OF RADIATION TOLERANCE RELATIONS Criteria. The bipolar is by far the most widely used transistor type. The usual criteria for hardening bipo-

Jan 1, 1970

By R. F. Mehl, R. F. Bunshah

A fast amplifier technique has been developed for the measurement of the rate of propagation of martensite in an Fe-29.5 pct Ni alloy. The time of formation of one plate of martensite is 3x10 sec and the rate of propagation is 3300 ft per sec approximately. IT has been known for some time that the plate-like structural unit of martensite forms from austenite with great rapidity. Wiester1 and Hane-mann, Hofmann, and Wiester took motion-pictures of the transformation as it occurs in a 1.65 pct C steel; they demonstrated that a single plate formed fully in the time interval between successive frames, viz., 1/20 sec, thus setting an upper limit. Forster and Scheil,3 using an Fe-Ni alloy with 29 pct Ni, recorded the sonic characteristics of the process electrically, upon an oscillograph, setting the upper time limit at 0.002 sec. Forster and Scheil,~ measuring the change in electrical resistance in the same alloy upon a cardiograph, set a limit of 0.02 sec. Forster and Scheil5 later, employing the same alloy, improved their technique, reporting an upper limit of 7.10 sec. In studying signals of such short duration, it is an important question whether the frequency response of the electrical system used is high enough compared to frequency of the pulse measured, or, put differently, whether the system is able to reproduce without distortion the signal arising, in this case, from the formation of a single martensite plate. Forster and Scheil (referring only to their last paper) obtained signals of a frequency of 30 kilocycles (hereinafter kc); this was about the frequency response of the equipment used; thus, if the signal had a frequency higher than 30 kc, it would still appear as a signal of frequency 30 kc. All of these results thus provided upper limits only. Recent developments in electronics have made available equipment with very high frequency response, very high sweep-speeds, high gain, etc. The electrical characteristics of such equipment, used in the present study, are given in Table I. Such equipment offers obvious attraction in the study of the rate of propagation of a martensite structural unit—and perhaps of other structural alterations proceeding at a very high rate. This paper reports an attempt to develop a technique employing such equipment to measure the time of propagation of a martensite structural unit and the variation of this with temperature, with the mode of formation—athermal and isothermal—in both polycrystalline and single-crystal samples; and from such measurements to obtain the rate of propagation. As will be seen, the results obtained are useful theoretically. Materials All data presented here are for an Fe-Ni alloy of the following analysis: 29.5 pct Ni, 0.027 pct C, 0.135 pct Mn, 0.094 pct Si, balance Fe. There were several reasons for choosing this alloy: 1—it is substantially the one used by previous investigators; 2—it exhibits both the athermala and the isothermal' mode of formation of martensite, both studied in detail by Machlin and Cohen; 3—the subzero temperatures of transformation in this alloy are experimentally very convenient; 4—it exhibits the "burst phenomenon";" 5—the change in electrical resistance upon the formation of martensite, a decrease, is great, approximately 50 pct.' The polycrystalline specimens were in the form of wires of 0.025 in. diameter; the single crystals were 1x1/4x1/4 in. Experimental Methods Electrical Apparatus: Fig. 1 is a schematic drawing of the electrical circuit used. The principle used in these measurements is the same as that used by Forster and Scheil." A small direct current, about 1 to 2 amp, is passed through the sample. When a martensite plate forms, the resistance of the sample changes and a high frequency signal is generated. This signal is picked up by the probes attached to the sample, fed into the bank of amplifiers and thence to the vertical deflection plates of a cathode-ray oscilloscope. The signal itself triggers the oscilloscope trace which flashes across the tube face and is photographed by means of a 35 mm movie camera at the end of a light-tight hood. The camera has no shutter. As soon as the signal flashes

Jan 1, 1954

By Pierre Hines

THE. Owyhee Tunnels in eastern Oregon were started in the early part of 1930, and were completed early in 1932, with the excep-tion of the Magoffin contract. One tunnel is a large water tun-nel, and the other is a small water tunnel; each is approximately tour miles long. Modern equipment was used to full advantage, and remarkably fast time was made during the driving period. The ,J. F. Shea Co., con-tractors, of Portland, Oregon, have broken established records in the smaller tunnel. Their methods are described in detail. The time of a complete round has been reduced by intelligent handling of mechanical shoveling, and this article records some of the useful facts developed. Charles A. Shea (president of the J. F. Shea Co., and secretary of The Six Companies, Inc.) not only granted permission to publish this article, but placed the company's complete daily reports at the writer's disposal. These reports were made out to conform with previous records upon important tunnel work, and enable a comparison to be made of actual averages, rather than ideal cycles, or representative cycles. Gilbert Shea, present superintendent, has been helpful with time, criticisms, and corrections of the information presented. Morton S. Boss, superintendent during the first 15 months of the tunnel work, gave many hours of his time during two visits lasting over two weeks. The whole staff of the J. F. Shea Co. has given encouragement and assistance.

Jan 1, 1933

By W. E. D. Stokes

The application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government rccords, 30 Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the railway at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a community of 1000 whites have been transported by airplane. A 31/2-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo. Many large American oil companies operated fleets of planes during 1936, ranging from fast, luxurious air liners for executives to elaborate geological prospecting units, ambulance planes, freight carriers and pipe-line repair crews. According to the U. S. Geological Survey, commercial firms photographed 16,291 square miles during 1935, while the Government compiled from aerial photographs by the Geological Survey in the United States 85,544 square miles. It was found that information could be determined in a fraction of the time required by surface methods. However, sounding a word of caution, a Commonwealth of Australia government report on aerial survey operations had this to say: It is necessary to repeat ad nauseam that aerial photographic survey is in no sense a substitute for geological investigation, though it is a very valuable adjunct thereto, and greatly facilitates and aceeleratcs geological mapping. There are many details

Jan 1, 1937

By Orville R. Lyons

CENTRIFUGAL force has been utilized for the dewatering of fine coal for over 50 years by means of machines commonly called centrifugal dryers. In any centrifuge the coal and water are subjected to a spinning action which usually inctedtocreases in intensity as the coal progresses through the machine. This spinning action, or the centrifugal force that it induces, tears water away from coal particles and produces a dewatered coal. The effectiveness of the dewatering action for any particular machine is governed by the size-consist of the coal and the centrifugal force imparted to the water on the coal. Four makes of centrifuge are currently being used to dewater fine bituminous coal in the United States. These include the vertical, basket-screen C.M.I. (Centrifugal and Mechanical Industries) Carpenter, Reineveld, and the horizontal solid-bowl Bird. The C.M.I. and Reineveld centrifuges are similar in construction and are variations of the Elmore centrifuge, varying principally in the slope of the basket, operating speed, size of perforations in the basket, and diameter of the basket. The same operating description suffices for both. These centrifuges are made up of two rotating elements, an outside conical screen frame and an inside solid cone which carries spiral pusher blades. The screen frame is supported by a hollow shaft, and the solid cone by a spindle shaft passing through the hollow shaft. Both the screen frame and the solid cone rotate at high speeds; the solid cone, with its scraping flights, rotating somewhat more slowly than the screen. The wet coal enters the machine at the top, falls on the cone, and is thrown against the screen by centrifugal force. The coal slides down the screen until it meets the upper end of the flights, where it is moved slowly along the flights until discharged at the bottom. The elfluent passes through the sieve basket or screen and discharges into a launder. The Carpenter centrifuge consists of a conical rotating element with a vertical axis, built up of three rows of perforated stainless-steel plates or stainless-steel wedge-wire or round-wire sections cut and rolled to conform to the surface of the cone. Wet material is delivered to a conical hopper inside the centrifuge casing and is distributed in a thin, even layer over the inner surface of the cone by a disk mounted on the rotor shaft. Impacting of the coal against the screen and the centrifugal force exerted as the material moves downwards creates a dewatering effect. The moisture is forced through the coal bed and then through the perforated plates of the basket, collecting in a circular trough built into the centrifuge. The effluent is conducted from the trough through the centrifuge casing by outlet pipes. The dewatered coal is discharged over the inside bottom edge of the rotor. The Bird centrifuge consists of a tank or truncated conical shell, which is revolved at the desired speed by means of a drive sheave. A screw conveyor rotates inside the cone or bowl at a slightly lower speed in the same direction of rotation. The feed entrance, in the center of the large end of the truncated cone, is high enough to allow formation of a pool of slurry. Adjustable effluent-discharge ports are located in the large end of the bowl so the level of the liquid can be regulated. The solids are moved forward by the screw conveyor as fast as deposited and carried above the level of the pool for an interval before leaving the bowl. In the past these four makes of centrifuge could be compared only by indirect means. The author published a rough comparison method in 1949' but

Jan 1, 1952

By L. O. Howard

The practice of using acid-lined converters at the plant of the Old Dominion, Copper Mining & Smelting Co. was discontinued early in January, 1913, and replaced by basic-lined converters. The new equipment consists of one electrically operated 12-ft. upright converter stand and two basic-lined shells for same. These shells are provided with twenty-four 1 1/4-in. tuyeres. The mouths are 5 ft. in diameter. Owing to the fact that there is no bedding system or other large storage capacity between the mine and the smelter, the furnaces must handle as fast as produced ore and concentrates, which may vary considerably from day to day, both in tonnage and copper content. Consequently the converter is often crowded to its utmost capacity by the frequent fluctuations in the daily matte supply. From the foregoing, it will be seen that in no way can the 'converter be favored by running light charges or by transferring to it from other stands in operation. Neither can it regularly be allowed to cool between blows, and only occasionally can it be run at as low a temperature as might be wished. No copper precipitate or other foreign material high in copper is available to help out the tonnage. Repairs and alterations or the removal of defective tuyeres must wait until such time as a slight falling off in.the matte supply allows the converting operations to ease up. These variable conditions all combine to interfere with the systematic operating of the converter. The first 12-ft. shell was blown in on Jan. 6, 1913, and ran until June 27, 1913, when it was removed to patch the brick. A record of operations covering this period follows: Shell No. 1. First Campaign, Jan. 6,to June 27, 1913 Commenced blowing............................Jan. 6, 1913. Taken off stand for patching.....................June 27, 1913. Total blowing time..........................2,689 hr. 40 min. Total number of, blows made.............................. 664 Average time of blow............................ 4 hr. 3 min. Tons matte charged.................................. 18,157 Average copper content of matte................ 43.9 per cent. Average time blowing one ton. copper................ 22.5 min. Total copper made............................... 7,250 tons

Jan 1, 1915

By Dorsey Hager

THE rapid increase of water troubles in the Mid-Continent oil fields is causing much alarm. Troubles occur at Towanda, Eldorado, Augusta, Cushing, Blackwell, and Healdton, although they had, not been acute in the Mid-Continent field until about two years ago, when the unusual conditions in the deeper oil fields were first encountered. California faced the same situation, but, thanks to aggressive measures, has largely overcome the dangers. The following analysis of water trouble may throw some light on the subject and be of assistance in solving the problems involved. WATER TROUBLES CLASSIFIED The presence of water in large quantities in oil sands has the following results: 1. Diminishes oil production. 2. Diminishes casing-head gasoline production: (a) By curtailing the gas flow. (b) By making the use of vacuum pumps unsuccessful. 3. Increases lifting costs: (a) By making it necessary to pump large quantities of water, which requires. a fast motion and long stroke (third hole). (b) By requiring the use of compressors for air lift. (c) By causing break-downs and delays due to the high speed necessary to pump water. (d) By making it necessary to treat "cut" or emulsified oil. Oil production is seriously curtailed by the presence of large quantities of water. Lease records show that wells are shut down 40 to 60 per cent. of the pumping time where serious water trouble occurs. While a small quantity of salt water may cut the paraffine and keep the oil moving, several hundred feet, or a hole full of water, effectually "kills" the oil

Jan 10, 1918

By Ellsworth Daggett

The Berlin gold-quartz mine is situated in Nye county, Nevada, on the west flank of the Shoshone range, about 40 miles south and 30 miles west from the town of Austin, the county-seat of Lander county. The distance from Austin is about 60 miles by stage-road. The outcrop of the vein, at the top of the incline-shaft, is situated just at the base of the mountain proper, almost exactly at the intersection of the mountain-side with the gravelly bench that slopes for about three-quarters of a mile to the flatter sage-brush plain, or desert valley, below. The vein itself consists almost entirely of quartz, with perhaps 2 per cent. of sulphide of iron, copper, lead, zinc and antimony, and perhaps a trace of some of the compounds of tellurium with gold and silver, although none of the latter have been as yet positively identified. The relative proportion, by weight, of silver and gold in the ores, varies in different parts of the vein, from 12 silver for 1 of gold, to 7 silver for 1 of gold. The quartz vein-filling is usually frozen fast to the walls, and is very hard and compact, seldom showing the friable, fissured, or shelly structure often to be found in quartz-veins. Comparatively little evidence of relative motion of one wall of the vein upon the other is to be found—a fact indicating that during the formation of the vein, and prior to the extensive movements herein described, little disturbance had taken place. No evidence whatever of metasomatic origin has been observed. On the other hand, occasional occurrences of comby structure, in which the axes of the quartz-crystals are at right angles to the plane of the vein, rather indicate deposition from solution in a pre-existing fissure. Spurs, or branches, and small parallel veins, while not en-

Jan 1, 1908

By Henry Fay

LAWRENCE ADDICKS, New York, N. Y., (communication to the Secretary *).-There are two points regarding gun erosion on which I want to say a few words: The first is about the analogy to hardening of wire by drawing and the second the possible role played by thermal conductivity of the metal. The ductile metals do not necessarily become brittle when cold-worked as it is possible to draw copper from 3. in. in diameter soft rod down to the finest hair wire without annealing. This results, as stated in the paper, informing a hardened core with a very hard skin. The electrical conductivity is depressed some 3 per cent. and the tensile strength nearly tripled. A soft copper wire 0.08 in. in diameter and 6 in. long may be twisted 150 or more turns before the wire will snap under torsion. A hard-drawn wire will break after perhaps a dozen twists, the skin breaking down at one spot. Just wiping the wire with a cloth clamp with dilute nitric acid has a remarkable effect in increasing the number of twists without appreciably lowering the tensile strength, showing the skin to be very thin. On the other hand, pickling the rod, from which the wire is to be drawn, in dilute nitric acid also greatly increases the number of twists which can be applied to the resulting wire. This indicates that the copper oxide scale produced when the wire bar is rolled hot is more or less rolled into the rod and may have much to do with the skin effect. We also know that if the conditions of drawing are not correct, the heat of deformation in the die may produce quite an annealing effect. The application of this analogy to what occurs in a gun to produce the effects noted offers some difficulty. The second point is that as the temperature of the surface of the gun bore has undoubtedly a great deal to do with the amount of erosion, one natural remedy would be to conduct the heat away fast enough to keep this temperature within desired limits. This brings up the question of the thermal conductivity of the metal of which the gun is made. We know that the conductivity of pure metals is greatly altered by alloying and that the alloy is usually, though not always, lower in conductivity than the metal before alloying. This is interesting when it is considered that the high-nickel and manganese-steel alloys show greater erosion as stated. Would it not be instructive to study the question from the point of view of heat conducted away from the eroded surface?

Jan 3, 1917

PRECEDING chapters on thermochemistry, and the reactions in and between metal and slag phases in the bath of the furnace tend to emphasize the equilibrium or "static" conditions in the furnace and process, such as the total amounts of heat from fuel combustion or from certain bath reactions, the concentration relationships between slag and metal at the steady state for certain reactions, and the like. Such data are obtained essentially by means of the logic of thermo- dynamics, which helps to determine the energy change between initial and final states in a process as well as to define its equilibrium or steady-state condition, but which is not concerned with the rate of change in the process or with the mechanisms or path followed between initial and final states. These questions of just "how it works" and "how fast" belong to the kinetic aspect of any process; their answers are helpful in speeding up or slowing down and thus controlling intelligently its operation, and also to understand certain natural limitations which are especially important in many high-temperature processes. The kinetic aspects of interest here comprise mainly (1) the flow of gases through the furnace system, (2) the flow of heat in the system, and (3) the mechanisms and rate factors in the various chemical reactions. A really adequate discussion of the first two subjects would require at least three or four times the space available here; it has been tried, therefore, in this and the next chapter to outline but a few fundamentals necessary to an intelligent approach and to indicate some of the conditions of heat and gas flow more or less peculiar to the open hearth, since several good general discussions on these subjects may be found in the literature.(1) For the designer of open-hearth furnaces, the principles of gas flow are of paramount importance.(2,3,4,5) They are also important to the operation of the process, however, at least to the extent of a general qualitative picture of the movement of gases in the system, which is all that is attempted here.

Jan 1, 1944