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By Nancy Estrada, Jane Nowell, Cathy Jennings, Debra Yniguez, Carol Lavery, Kristin Harrer

Pilots of the MH-60S helicopter are exposed to continuous whole body vibration (WBV). Pilot fatigue is a growing operational concern due to the increased frequency of extended durations of missions (6-8+hours) in support of Operations Iraqi Freedom and Enduring Freedom. Endurance aspects of the currently used rotary wing seating systems were not optimized for the longer missions and wide range of pilot anthropometric measurements, which is now typical of naval aviation. The current seating systems were designed primarily to meet crashworthiness requirements, not for the wide range of pilot anthropometry or to mitigate WBV. Albeit, an issue, pilot fatigue and reduced mission effectiveness are also critical concerns. Current Hazard Reports indicated that pain in pilots’ legs and backs begin two to four hours into the flight and increase with time. Mission readiness also decreases with an increase in flight duration due to the constant distraction of pilots shifting in their seats while trying to get comfortable. Froom, et al [2] reported a dose-response relationship between the length of military helicopter flights and back discomfort. He also concluded that this pain is typically dull, over the lower back, and its prevalence and intensity are dependent on the total flight hours of exposure. Methods This study evaluated WBV produced in the pilot seating systems onboard the MH-60S. The purpose of the study was to test and compare the effectiveness of two different seat cushions, the current seat cushion versus an anti-vibration seat cushion. Both seat cushions were measured for acceleration levels averaged over five-minute intervals using a triaxial seat pad accelerometer. The recordings were completed for a 3-hour straight and level flight. A frequency analysis from 0-80 hertz (Hz) was conducted on all acceleration measurements to determine the dominant axis and frequency of the pilots’ vibration exposure. The results were then compared to the applicable Threshold Limit Values (TLVs) established by the American Conference of Governmental Industrial Hygienists (ACGIH) [1] and the International Organization for Standardization (ISO) 2631.1 [3] to determine the MH-60S pilots’ permissible exposure time for both seat cushions. Results The results of the study showed that for both seat cushions the vibration levels of the z-axis at 16 Hz had the shortest allowable exposure duration, according to the ACGIH TLVs. In the z-axis at 16 Hz, the MH-60S’s current seat cushion’s acceleration levels indicated an exposure time limit of approximately 6 hours, while the anti-vibration seat cushion’s acceleration levels pierced the 8-hour exposure time limit curve. This is shown in the graph below.

Jan 6, 2006

By Lindsay D. Norman

Computer models for simulating the construction and for calculating the properties of particulate solids in two- and three-dimensional systems (coverings of circles and packings of spheres, respectively) were developed. By simulating the physical process of constructing circle coverings and sphere packings, in which the circles or spheres were randomly selected from many different distributions of sizes, physically realizable loose random assemblies were simulated whose physical and geometrical properties were predictable with the computer. Many of these properties, such as the number of contacts, are extremely-difficult to measure accurately, or considerable ingenuity is required in their determination. All of these properties were easily and accurately calculated by the computer models for many different coverings and packings constructed from equal, discrete, uniform, and log-normal distributions of particles. In addition to the loose random assemblies, dense random covering and packing constructions were simulated whose properties are ideal upper limits for those of the loose random coverings and packings. The properties of the dense random coverings and packings, heretofore only obtainable by theoretical analysis, were also simply obtained. The statistical geometry of loose random coverings and packings was studied, and several new interpretations of the area-covering or space-filling requirements in these systems were made. In two dimensions, it was found that the properties of all loose random coverings are predictable by taking suitably weighted averages of the corresponding properties of just four kinds of polygons whose edges are defined by connecting the centers of mutually tangent circles in the covering. The distributions of these polygons that permit area-covering were determined, and empirical equations for predicting the density, average coordination number, and average pore area in loose and dense random coverings were formulated. The properties of loose packings were determined by performing a simplicial division of the computer-simulated assemblies to produce a unique set of minimum volume, space-filling tetrahedra whose edges connected the sphere centers in each packing. A simple empirical equation was formulated that permits the calculation of the average number of contacts in any sphere packing, random or regular. Some of the statistical geometrical properties of the simplicial tetrahedra in the computer-simulated packings were analyzed. The tetrahedron edge length distributions in all the loose random packings were nearly identical when the edges were presented in terms of sphere diameters, regardless of the sphere population in the packing. Moreover, the gap lengths in the loose packings were to an excellent approximation representable by a uniform distribution of sizes. The distributions of spheres in tetrahedra resulting from the simplicial division of the loose random packings also existed in the tetrahedra in dense random packings. These observations were employed in developing a unique method for predicting the geometrical properties of loose random packings without simulating the assembled packing. Instead, the space-filling simplicial graph could be predicted for any given density of packing of any sphere population. The cumulative packing properties of these tetrahedra were shown to be nearly identical to those calculated by all loose random packing simulations attempted in this investigation. The simplicial tetrahedra completely describe a packing and can therefore be used to predict all properties of interest.

Jan 1, 1971

By G. W. Jones

The results presented in this report deal with the elimination of explosion hazards of ether-oxygen mixtures by the addition of helium. The method is based upon the fact that every combustible gas, vapor, or dust will not burn or explode when the oxygen content of the mixture is reduced below certain definite values. These critical oxygen values are usually different for each combustible, varying with the percentage of the combustible present in the mixture and also with the inert gaseous material used to reduce the oxygen content of the mixture.

Jan 1, 1941

By G. W. Jones

The results presented in this report deal with the elimination of explosion hazards of ether-oxygen mixtures by the addition of helium. The method is based upon the fact that every combustible gas, vapor, or dust will not burn or explode when the oxygen content of the mixture is reduced below certain definite values. These critical oxygen values are usually different for each combustible, varying with the percentage of the combustible present in the mixture and also with the inert gaseous material used to reduce the oxygen content of the mixture.

Jan 1, 1941

By John Organiscak

A majority of continuous mining machines employ a water spray system and a machine mounted flooded-bed scrubber to suppress and capture dust during coal mining. These machine mounted dust control systems must be designed to function within the localized face ventilation system at the mining section to control both dust and methane. Spray systems can impede or improve the scrubber effectiveness in controlling dust or methane at the mining face. Laboratory experiments were conducted to examine the effect of spray type, spray pressure, machine body blocking sprays, and scrubber airflow on dust and gas levels while using a 12.2 m (40 ft) exhaust ventilation curtain setback from the face. These experiments were conducted with the mining machine positioned at the end of a simulated 6.1 m (20 ft) sump and slab cut. Results indicate that the hollow cone nozzles with blocking sprays best complemented the flooded-bed scrubber performance in an exhaust ventilation system. This external spray system notably reduced dust and gas levels on the off-curtain side of the mining machine for both the sump and slab cut as compared to the flat spray nozzles. Higher scrubber airflows reduced dust and gas levels on the curtain side and in the return of the continuous mining machine. The remote operator position, located on the off curtain side and parallel to the inlet end of the exhaust curtain, sustained the most stable and lowest dust levels around the mining machine.

Jan 1, 2010

By Arturo Ressi di Cervia

The utilization of diaphragm wall construction in Hong Kong began in 1974 with the construction of the New World Center, the first diaphragm wall job built in the British Colony. That landmark job of which I am presenting a few slides and a schematic description, embodied all of the difficulties and problems which are encountered in the difficult geology of Hong Kong. A small rocky island in the South China Sea, Hong Kong provides one of the finest natural harbors in the world. It is its splendid harbor, coupled with the enterprising attitude of the Hong Kong Chinese and the laissez-fair attitude of the British government which has resulted in the explosive growth of this speck of land soon to revert to the political control of mainland China.

Jan 1, 1993

By Bosco Poon, Kim Chan, Luis Raúl Castañeda, Geoff McKay

"Driven steel tubular piles of up to 2 m diameter have been used to support abutments and piers of a bridge over Nambucca River and floodplain. The bridge was designed by Arup-Aurecon Design Joint Venture (Lead Designers) with GHD leading the geotechnical design assessment in conjunction with Acciona Ferrovial Joint Venture (AFJV – Principal Contractor). Piles were to be driven through alluvium and founded on foliated Phyllite bedrock. The large diameter piles posed significant challenges on bearing capacity assessment and pile acceptance criteria, especially for anisotropic rock strength. Prior to pile driving, boreholes were drilled at each pile location, accompanied with a suite of rock index and UCS testing. AFJV and GHD oversaw geotechnical construction verification. All production piles were monitored with a Pile-Driving-Analyser to manage driving stresses and pile termination. Wave matching CAPWAP analyses were performed on 40% of the piles at the end-ofdrive, or restrike, to satisfy specification requirements and limit over-driving. This paper presents discussions on the design and construction of the driven piles with findings from the extensive dynamic pile data obtained. Based on the shaft resistance distribution and toe resistance obtained from CAPWAP analysis, the mobilised pile shaft frictions fs of the soil / rock materials, as well as the end bearing fb of the founding Phyllite bedrock, are examined. The impact of the rock fabric foliation angle on the m obilised fb, and the relationship between rock strength and the mobilised fs are outlined.INTRODUCTIONThe Bridge over Nambucca River consists of a single bridge structure, comprising single substructures and separate superstructures. The 850 m long bridge facilitates the crossing of the Northbound and Southbound carriageways of the Pacific Highway Upgrade over Nambucca River, with central median barriers, separated by a horizontal clearance of 50 mm. The bridge is required to span over the Nambucca River, which is a navigational channel, and over the adjacent floodplains, including two local access roads and the existing Pacific Highway. The bridge superstructure consists of 21 simply supported spans, each comprises four 2.25 m deep precast post-tensioned U-Girders, with two girders across the width of each carriageway. The spans of girders vary from eleven spans of 39.5m and ten spans of 41.5 m. The floodplain section of the bridge was founded on up to 2m diameter steel tubular piles, designed to be driven through alluvial sediments and weak rock to nominal refusal on sound rock. Dynamic load testing using wave matching CAPWAP (CAse Pile Wave Analysis Program) analyses in conjunction with PDA (Pile Driving Analyser) were used to verify the pile integrity and mobilised capacity. This paper discusses geotechnical aspects associated with design and construction of driven piles. The methodology developed for construction to verify pile capacity and to meet acceptance criteria is outlined. Based on the shaft resistance distribution and toe resistance obtained from CAPWAP analysis, the mobilised pile shaft friction, fs of the soil / rock materials, as well as the end bearing, fb of the founding Phyllite bedrock, are examined. The impact of the rock fabric foliation angle on the mobilised fb, and the relationship between rock strength and the mobilised fs are outlined."

Jan 1, 1900

By M. Hozayen, Q. Ni, E. S. Radwan, P. Nawrocki, A. Jebbouri

"A major geomechanical study was conducted for one of the UAE onshore oil fields with the purpose of studying reservoir rock properties and stress distribution, based on which a 3D coupled reservoir geomechanical model was built. This model was later used for wellbore stability analysis and for analyzing the effect of fractures on future reservoir production performance, including fracture deformation and permeability evolution occurring due to reservoir depletion and resulting changes in local stress field. The subject of this study was a complex fractured Upper Cretaceous carbonate reservoir characterized by high degree of heterogeneity, both vertically and laterally. Wellbore instability related drilling problems were encountered while drilling the wells in this field. The problems were mainly in drilling the horizontal wells, including breakouts and mud losses. Experimental results of laboratory tests used in this study are summarized in Part I of this paper whereas wellbore stability analysis and formulation of a3D geomechanical model that was built for that purpose is summarized herein.A 3D geomechanical reservoir model was developed, which included natural fractures. The mechanical properties of the reservoir rock, such as Young’s modulus, Poisson’s ratio, UCS, friction angle and tensile strength were populated based on the correlations established in Part I of this paper and the developed model was then used to simulate the 3D mechanical-property distribution and the evolution of the in situ stresses in the field due to depletion from 1983 to present-day. Based on the full field model, mud weight cubes were developed to predict the safe mud weight windows in different drilling directions. In addition, well stability prediction for two planned wells was performed using a 3D near-borehole model. Firstly, the computed stress state and mechanical properties simulated in the full field model were extracted along the well trajectory of an existing horizontal well which was drilled recently and then, a3D near-borehole model was constructed along the well trajectory. The wellbore stability analysis along the well trajectory, including stress state, strain distribution and displacements, was performed to identify the instability events along the well trajectory. It has been seen that the presence of natural fractures is closely related to the recorded borehole instability incidents. The computed plastic strains which indicate the wellbore failure were consistent with the recorded wellbore instability events in the FMI image logs, what provide further verification of the developed model. Then, this 3D near-borehole model was applied to two planned horizontal wells and the wellbore stability analysis for the two wells was carried out.The results showed that drilling vertically in the reservoir is safer than drilling horizontally. However, the drilling mud weight window in the vertical direction is narrow, being as narrow as 18.7 pcf or 0.299 sg locally. Drilling horizontally is less stable towards the maximum far field stress direction than towards the minimum far field stress direction. The mud weight cubes were used to identify the optimal well placement and well trajectory. For planned well trajectories, this technology can also be used to determine the optimal mud weight."

Jan 1, 2015

By J. A. Jaekel, W. C. Aitkenhead

Uranium deposits in the Spokane Indian Reservation, as well as those around Mt. Spokane, are essentially low grade, much of the ore containing less than 0.2 pct U3O8. The Mining Experiment Station of the Division of Industrial Research, State College of Washington, has been engaged in intensive research on the amenability of these low grade ores to froth flotation. The results: successful flotation of autinite, chief mineral constituent. At the outset of this work the goal was a concentrate of 1 pct U3O8 with a 90 pct recovery from ores containing less than 0.2 pct U3O8. Most of the work has been done on argillite ore from the Midnight mine on the Spokane Indian Reservation. The goal has not been attained using this ore, but samples of the granite ore from Mt. Spokane yielded successful results. For example, a concentrate containing 11.2 pcl U3O8 was produced from a Mt. Spokane high grade ore containing 1.27 pct U3O8 with a recovery of 97.8 pct. Another Mt. Spokane ore yielded a concentrate of 5.0 pct U3O8 from an ore containing 0.13 pct U3O8. with a recovery of 85 pct. This same ore gave a recovery of 93.5 pct when the grade of concentrate was reduced to 2.0 pct. It has been concluded that a successful method for floating autunite has been developed and that the mediocre results from the Midnight argillite ore are probably caused by the presence of some other uranium mineral or minerals less amenable to these reagents. The experimenters tested a third type of Washington ore, found on the Northwest Uranium Mines Inc. property on the Spokane Indian Reservation. This is a conglomerate of pebbles and small boulders of partially decomposed granite and is shot through with autunite. Its characteristics lie between those of the Midnight ore and the granite ore from the Spokane district. It responds better than the ore from Midnight but not as well as that from Mt. Spokane. As the fatty acids are the only type of collectors showing promise, investigation has been concerned with these acids and the optimum conditions for their use. The first method for treating the argillite ore from the Spokane Indian Reservation made use of Cyanamid's R-708 as a collector, a tall oil product described as a substitute for oleic acid. Although the investigators proved that R-708 is a collector for autunite when mixtures of autunite and silica sand are used, results on the ore were mediocre. Tests of other fatty acids revealed that the solid fatty acids of the saturated series are collectors for autunite and that their collecting power increases with the length of the carbon chain. The even carbon members of the whole series were tested from the 10 carbon acid (capric) to the 22 carbon acid (be-henic). The least expensive collector, stearic acid (18 carbon), proved to be a good one, so this was used in most of the tests. In first attempts with stearic acid, the collector was dissolved in various hydrocarbons and the solutions were added to the flotation cell. Cyclohexane, gasoline, fuel oil, kerosene, and other solvents were tried. Small amounts of high grade concentrates could be brought up, but recoveries were low. Finally emulsions of stearic acid were tried. It was discovered that stearic acid alone has little collecting power except when conditioning is carried out at high temperature. When hydrocarbon solvents were also present, it proved to be an excellent collector. An example of one emulsion that proved satisfactory for some ores is given as follows: 1 part stearic acid by weight, 1 part sodium oleate by weight, 1.2 parts kerosene by weight, 100 parts water. In some successful tests part of the stearic acid was replaced by oleic acid. The emulsions were made by agitating the stearic acid and sodium oleate together with hot water, then adding the kerosene and agitating while cooling. In the five tests reported in Table 1, 650 g of ore were ground with 650 cc water in a laboratory rod mill. The pulp was filtered to eliminate excess water and the ground ore transferred to a stainless steel beaker for conditioning at high pulp density. In most of the tests sodium hydroxide was added to the conditioner during agitation, then the collector emulsion, and finally the sodium silicate. The amount of alkali was adjusted to give a pH of 8.5 to 9.0 in the flotation cell. After conditioning the pulp was transferred to a laboratory flotation cell and the test completed in a normal manner. It is interesting to note that a deposit of high grade concentrate forms on the conditioning agitator and in the conditioning vessel, and at times on the agitator of the flotation cell itself. A few grams of concentrate running as high as 4 pct U3O8 were recovered from the conditioner when Midnight ore containing less than 0.2 pct U3O8 was treated. In the examples given in Table I this conditioner concentrate is calculated as part of the total concentrate. The authors have not yet fully explored the possi-

Jan 1, 1960

By P. A. Laxen, H. R. Spedden, A. M. Gaudin

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface1 are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.2,3 Study of the adsorption of sodium from an aqueous solution on quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained.4,5 Three main factors which appeared likely to affect the adsorption of sodium are: 1-concentration of sodium in the solution, 2-concentration of other cations in the solution, and 3-anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in the amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxylion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory4 except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying5 To minimize the laborious preparation of quartz, experiments were made to determine whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na' activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot II) and 2000 (lot III) as determined by the Bloecher method.6 Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.7 It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß radiation and a 1.30 mev ? radiation. The decay scheme is illustrated in the following equation: [Y Nam S. - 'Net 3 years] The ß radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang8 The original active material was 1 ml of solution containing 1 millicurie of Na22 as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen5 In brief, it included the following steps: 1-Ascertainment of linearity between concentration of Na22 and activity measured. 2-Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3-Taking precautions to avoid evaporation of water during centrifuging.

Jan 1, 1952

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

By W. W. Vaughn, R. H. Barnett, E. E. Wilson

Soon after the search for uranium ores on the Colorado Plateau began in earnest, thousands of feet of drill core ranging from 1 1/8 to 2 1/8 in. diam became available for study. Although significant advances had been made in the technique of quantitative gamma-ray borehole logging, instrumentation was in the development stage, and complete reliance could not be placed on gamma-ray logs alone to interpret quantitatively the meaning of radioactivity in a drillhole. A method that would be faster than chemical analysis and still give reproducible and reliable results for various drill core sizes was desirable to provide additional information on the enormous footage of drill core being accumulated. A solid phosphor scintillation drill core scanner was designed and constructed. Basically the instrument was developed to measure radiation from a drill core which would not be clearly recorded by a gamma-ray logger using a Geiger tube as the sensitive element. Such data would be beneficial in constructing isorad maps to delineate ore-bearing zones. A calibration in the range 0.01 to 0.1 pct eU.,O, was provided; above 0.1 pct eU3O8 gamma-ray logs were available and were being used to calculate grade and tonnage of ore reserves. The core scanner, however, has been used to estimate equivalent uranium content of ore-grade materials containing as much as 2.2 pct eU3O8 with an accuracy of ± 10 pct, the sample being in the form of a BX drill core. Actually, an apparent calibration of eU3O8 vs counts per unit time is a straight line with a slope that is a function of the sensitive element and the geometry of the counting assembly. A true calibration that will show the expected departure from a straight line is due principally to the random nature of the pulse from a radiation source and the nonlinearity of the electron circuitry. Design and Construction: Three methods of detecting radioactivity were considered and applied in developing the core scanner now in use: 1) the Geiger tube, 2) liquid scintillation phosphors, and 3) solid scintillation phosphors. The desired sensitivity and long-term drift characteristics needed for this operation could be attained only by using solid scintillation phosphors. All three methods are discussed. Before scintillation counters were common, nine beta-gamma sensitive Geiger tubes 7/8 in. diam by 12 in. long were used, arranged to surround the drill core with tube axes parallel to the axis of the core. This arrangement of Geiger tubes was en- closed in a lead shield 1 in. thick, and provision was made to slide a 6-ft length of drill core manually into the counting chamber, one foot at a time. A count for each segment was taken with a scaler while the core remained stationary. The equivalent uranium content of the different sections of drill core could then be estimated with the aid of a calibration curve of counts per unit time vs percent equivalent uranium (eU). In rare cases the effects of the radioactivity concentrated in small areas within the core introduced errors in the readings made with the Geiger tube arrangement owing to the geometry of the measurement. The variability of counting rate due to a localized concentration of radioactivity in a spot in the wall of a drill core is illustrated in Fig. 1. This effect and the inherent low efficiency of the Geiger tube were considered major disadvantages of this counting arrangement. When liquid scintillation phosphors became available the core scanner in Fig. 2 was constructed to make a more accurate measurement of the equivalent uranium content of a sample. This instrument contains about 4 liters of liquid phosphor in a stainless steel coaxial cylinder 1 ft long, with inner and outer walls 0.060 in. and 0.125 in. thick, respectively. Four end-window type photomulti-plier tube with cathodes of 2 in. diam, immersed in the solution at right angles to the axis of the core, were used to observe light flashes in the phosphor. The liquid phosphor offered equal sensitivity to radiation originating at any point in the enclosure and represented geometrically the optimum in design. However, providing a semi-permanent leak-proof seal between the glass envelope of the phototube and the metal walls of the container proved to be a serious problem in constructing the equipment. The most effective seals were especially machined O-rings from sections of large tygon tubing. The tygon took a permanent set owing to cold flow characteristics and in most cases sealed completely. The light absorption characteristics of the liquid phosphor changed gradually with time, and after one month the counting rate had decreased to half the original value. The most sensitive liquid phosphor tested proved to be a solution containing 4 g of 2.5-diphenyloxazole and 0.01 g of 2-(1-naphthy1)-5-phenyloxazole per liter of toluene. With fresh solution in the chamber and with all photomultiplier tubes operating in parallel, the counting rate contributed by any one of the four photomultiplier tubes was about 85 pct of the counting rate from a single tube operated individually. From these observations it was concluded that owing to coincident loss and light attenuation within the liquid phosphor, the apparent sensitivity could not have been materially increased by additional phototubes. However, this approach to core

Jan 1, 1960

By Denis G. Maxwell

INTRODUCTION It is my intention in this paper to deal with gold, uranium, diamonds, platinum, manganese, chrome, vanadium and heavy mineral sands. These are the most important strategic minerals produced by the Republic of South Africa which are not covered in other sessions of this program. In each case I have high- lighted the statistics and peculiar advantages which combine to make South Africa a vital source of these minerals. Before proceeding to give individual attention to these minerals I believe it would be useful to define what I mean by 'strategic'. The Concise Oxford Dictionary defines strategic in the context of materials as 'essential for war'. However it is commonly used in a much broader sense than this (often, in fact, very loosely) and I prefer to define it as 'concerned with the acquisition and maintenance of power, whether economic, political or military.' A VITAL SOURCE In dealing with the individual minerals I have quoted statistics which are contained in Tables 1, 2 and 3. Table 1 clearly shows the absolute size of the South African mineral industry. However, it can also be used to demonstrate the importance of the industry to the South African economy if compared with the GNP in 1980 of about R60 billion. Table 4 illustrates clearly how important South Africa is as a supplier of these minerals to most of the important industrialized countries of the Western World. Gold If anyone had any doubts about the inclusion of gold in a list of strategic minerals I am sure that the above definition of 'strategic' will convince them that it certainly belongs there. Similarly no one is likely to have any doubt about the fact that South Africa is a vital source of supply. Tables 2 and 3 show that in 1980 we had 51% of the world's reserves and accounted for 55% of world production. The figures for the Western World are considerably higher. The only other major producer, of course, is Russia, with small but significant production in the Pacific Rim area coming from Australia, Canada, Latin America, Papua New Guinea, Philippines and the U.S. All South African mine gold production is shipped in bullion form containing about 88% gold and 9% silver to the Rand Refinery which is a modern refinery with large scale units capable of refining half a ton of bullion at a time. The Refinery is equipped to produce standard 'good delivery' gold as well as 9999 gold and 999 silver. The Refinery also produces the 22 karat blanks which are, used by the South African Mint to produce Kruger Rands. It goes without saying that the South African gold mining industry leads the world in all aspects of deep-level, narrow-reef mining technology. The industry's metallurgists, too, have a record of tenacious and continuing efforts to improve extraction to the level of the present finely honed efficient process used on all the modern mines. Uranium In 1980 South Africa had 14% of the uranium reserves of the Western World and accounted for 14% of production. In view of the paucity of data I am not in a position to estimate figures for the total world. All the other major sources of uranium in the Western World are situated around the Pacific Rim, with the U.S. and Canada already being major suppliers and accounting for 38% and 17% of Western World production in 1980. Australian production at the time was small but they have very large reserves and production is already rising rapidly. The U.S., Canada and Australia account respectively for 22%, 19% and 29% of the uranium reserves of the Western World. South Africa has been a major producer continuously for 30 years. Nearly all the uranium produced, amounting to about 115 000 tons up to the end of 1981, was a by-product or co-product of gold extraction. During that time the industry has frequently led the world in technological innovation, and has established a reputation as a reliable producer of a consistent, high-grade product. In the latter respect, it is helped by the fact that production is marketed by one company, Nuclear Fuels Corporation, which also blends, dries and calcines the product from the individual mines and samples and assays it before shipping. Diamonds Diamonds are the rock on which the South African mineral industry is founded. The discovery of diamonds in 1866 gave rise to the first major mineral industry in the country and the profits from diamond mining helped to finance the gold mining industry 20 years later. Although now overshadowed by gold, diamonds are still very important in the overall picture of mineral production and exports, as can be seen in Table 1. There are really three separate diamond markets - gem, natural industrial, and synthetic - and, to be meaningful, statistics should be provided separately. Unfortunately separate figures are not available. The figures in Tables 2 and 3 show that, for gem and natural industrial together, South Africa ranks third in the world in production and second in reserves. South Africa is a major producer of synthetics and probably ranks second in the world after the U.S. Recently, of course, Australia was the scene of a major diamond discovery and will soon become the only

Jan 1, 1982

By D. T. Peters, S. Floreen

The age hardening behavior of an Fe-8Ni-13Mo alloy was studied after the matrix had been varied to produce either ferrite, cold u~orked ferrite, or nzassive nzartensite. The aging behavior of the cold worked ferrite and murtensite structures were very similar. The martensite aging kinetics were much different from those observed in earlier studies of aging of maraging steels, even though the martensite wzatri.r had the same dislocation structure as those found in maraging steels. The results suggest that the previously observed precipitation kinetics of maraging steels ?nay have been controlled by the nucleation be-haviov, which in turn were dictated by the alloy compositions and the resultant identities of the precipitating phases. IT is well known that the rate of precipitation from solid solution depends not only on the degree of super-saturation, but also on the density and distribution of dislocations in the matrix structure. These imperfections often act as nucleation sites, and may also enhance atomic mobility. 'Thus, the presence of dislocations is important since the type and distribution of precipitates may be determined by them. The precipitate density and morphology in turn affects the mechanical properties of the alloy. A number of studies have been devoted to the precipitation characteristics in various types of maraging steels.'-" These are iron-base alloys containing 10 to 25 pct Ni along with other substitutional elements such as Mo, Ti, Al, and so forth, that are used to produce age hardening. The carbon contents of these steels are quite low, and carbide precipitation is not believed to play any significant role in the aging reactions. After solution annealing and cooling these alloys generally transfclrm to a bcc lath or massive martensite structure characterized by elongated martensite platelets that are separated from each other by low angle boundaries, and that contain a very high dislocation den~it~.~~~~~~~~-~~ Age hardening is then conducted at temperatures on the order of 800" to 1000°F to produce substitutional element precipitation within the massive martensite matrix. Most of the aging studies to date have revealed several common traits in these alloys, regardless of the particular identity of the precipitation elements. Generally hardening has been found to be extremely rapid, with incubation times that approach zero. The agng kinetics, at least up to the time when reversion of the martensite matrix to austenite begins to predominate, frequently follow a AX/~~ = ktn type law, where x is hardness or electrical resistivity, t is the time, and k and n are constants. The values of n are frequently on the order of 0.2 to 0.5, which are well below the idealized values of n based on diffusion controlled precipitate growth models. Finally, the observed activation energy values are typically on the order of 30 kcal per mole, and thus are well below the nominal value of about 60 kcal per mole found for substitutional element diffusion in ferrite. The common explanation of these observations is that the precipitation kinetics are controlled by the massive martensite matrix structure. Thus, the absence of any noticeable incubation time has been attributed, after ~ahn," to the fact that the precipitate nucleation on dislocations may occur without a finite activation energy barrier. The low values of the activation energy are generally assumed to be due to enhanced diffusivity in the highly faulted structure. If this explanation that the precipitation kinetics are dominated by the matrix structure is correct then one should observe a distinct difference in lunetics between aging in a martensitic matrix and aging the same alloy when it has a ferritic matrix. Such a comparison cannot be made with conventional maraging compositions, but could be made with the alloy used in the present study. In addition, the ferritic structure of the present alloy could be cold worked to produce a high dislocation density so that one could determine whether ferrite in this condition would age similarly to martensite. EXPERIMENTAL PROCEDURE The composition of the alloy used in this study was 8.1 pct Ni, 13.0 pct Mo, 0.10 pct Al, 0.13 pct Ti, 0.012 pct C, bal Fe. The alloy was prepared as a 40 lb vacuum induction melt. The heat was homogenized and hot forged at 2100°F to 2 by 2 in. bar, and then hot rolled at 1900°F to $ in. bar stock. The aging lunetics were followed by Rockwell C hardness and electrical resistivity measurements. Samples for hardness testing were prepared as small strips approximately 2 by $ by 4 in. thick. Electrical resistivity was studied on cylindrical samples approximately 2 in. long by 0.1 in. diam. The method for making the alloy either martensitic or ferritic was based on the fact that the alloy showed a closed y loop type of phase diagram. At high temperatures, above approximately 24003F, the alloy was entirely ferritic. Small samples on the order of the dimensions described above remained entirely ferritic after iced-brine quenching from this temperature. In practice, a heat treatment of 1 hr in an inert atmosphere at 2500°F followed by water quenching was used to produce the ferritic microstructure. These samples were quite coarse grained and usually en-

Jan 1, 1970

By T. R. A. Davey

IN 1947 the author became interested in the fundamental aspects of the desilverizing of lead by zinc, conducted some experimental work, and searched the technical literature for all available fundamental data. Since then a revival of interest in the subject in Europe resulted in the appearance of quite a number of papers. It became evident that it would be more profitable to collect together and examine thoroughly the results of various workers, than to attempt to duplicate the experimental determinations. There are many inconsistencies in the various publications, and it is opportune to review at this time the present status of knowledge on the Ag-Pb-Zn system. There is also a need for a clear description, in fundamental terms, of the various desilverizing procedures. This paper is presented in four sections: 1—There is an historical review of the origins of the Parkes process, of the results of many attempts to find a satisfactory fundamental explanation for the phenomena, and of the modifications proposed to date. 2—A diagram of the Ag-Pb-Zn system is presented. This is believed to be free of obvious inconsistencies or theoretical impossibilities, although thermodynamic analysis subsequently may reveal errors. 3—The fundamental bases of the various desilverizing procedures, which have been used up to the present day, are described; and a new method is suggested for desilverizing a continuous flow of softened bullion in which the bullion is stirred at a low temperature in two stages producing desilverized lead at least as low in silver as that from the Williams continuous process and a crust which, on liquation, yields a very high-silver Ag-Zn alloy. 4—A suggestion is made for the revival of de-golding practice, following a recently published account which does not seem to have attracted the attention it deserves. The terms "eutectic trough" and "peritectic fold" as used in this paper are synonymous with "line of binary eutectic crystallization" and "line of binary peritectic crystallization" as used by Masing.' The German literature on ternary and higher systems is rather extensive and a fairly general system of nomenclature has arisen, whereas in English usage the corresponding terms are not as well established. For this reason the meanings of terms used in this paper, together with the equivalent German terms, are given as follows: 1—Eutectic trough—eutektische rinne: line at which a liquid precipitates two solids S1 and S2 simultaneously. If the composition of a liquid which is cooling reaches this line, it then follows the course of this line until a eutectic point is reached, or until all the liquid is exhausted. The tangent to the eutec-tic trough cuts the line joining S1S2. 2—Peritectic fold—peritektische rinne: line at which a solid S1 and a liquid L transform into another solid S2. If the composition of a liquid which is precipitating S1 reaches the line, on further cooling only S2 is precipitated. The liquid composition moves from one phase region (L + S1) into the other (L + S2), and does not follow the course of the boundary. The tangent to the peritectic fold cuts the line S1S2 produced nearer S,. 3—Liquid miscibility gap, or conjugate solution region—mischungslucke: the region within which two liquid phases coexist in equilibrium over a certain range of temperature. A system whose composition is represented by a point in this region comprises one liquid at high temperature; then as the temperature is progressively reduced, two liquids, one liquid and one solid, one liquid and two solids, and finally three solids. 4—Liquid miscibility gap boundary—begrenzung der flussigen mischungsliicke: the line along which the surface of the miscibility gap dome, considered as a solid model, intersects the surrounding liquidus surfaces. 5—Tie lines—konoden: lines joining points representing the compositions of two liquids, a liquid and a solid, or two solids, in equilibrium. In binary systems the only tie lines customarily drawn are those through invariant points, e.g., through the eutectics of the Pb-Zn and Ag-Pb systems, or the various peritectics of the Ag-Zn system, as in Figs. 1 to 3. In ternary systems it is desirable to draw sufficient tie lines to indicate the slopes of all possible tie lines. 6—Ternary eutectic point—ternares eutektikum: point at which liquid transforms isothermally to three solids, S1, S2, and S Such a point can lie only within the triangle 7—Invariant peritectic (transformation) point— nonvariante peritektische umsetzungspunkt: (a) — On the miscibility gap boundary, the point at which two liquids and two solids react isothermally so that L, + S, + L, + S2. (b)—On the eutectic trough, the point at which a liquid and three solids react iso-thermally so that L + S, + S2 + S3. Such a point must lie on that side of the line joining S,S which is further from S,. (c)—A further possibility, not found in this ternary system, is that the point is at the intersection of two peritectic folds when the reaction concerned is L + S, + S, + S Historical Introduction Karsten discovered in 1842 that silver and gold may be separated from lead by the addition of zinc.2 Ten years later Parkes used this fact to develop the well known desilverizing process which bears his

Jan 1, 1955

By J. J. Jonas, G. Gagnon

SHG zinc was extruded in the temperature range 110" to 350°C and the strain rate range 0.05 to 5 sec-1 The strain rate/flow stress/temperature results were analyzed using a power sinh stress relationship. When temperature changes due to the heat of deformation and to heat losses are neglected, the exponent of the sinh function of the stress is 5.6, and the apparent activation energy of deformation is 28 kcal per mole. When these changes are taken into account, the exponent decreases to 4.7 and the activation energy to 23 + 2 kcal per mole. The corrected stress exponent and activation energy are in very good agreement with published values obtained from creep experiments, and suggest that the hot extrusion of zinc is controlled by a mechanism involving self-diffusion. When the extrusion and creep data are compared using a Zener-Hollomon parameter and either a sinh or an exponential stress term, an appreciable offset is observed, which may be due to the difference in impurity content. For a given set of extrusion conditions the ram speed, maximum pressure, and initial temperature can also be correlated using a Zener-Hollomon parameter and a sinh pressure term. THE deformation of metals at temperatures over about one-half the absolute melting temperature has been extensively studied at creep strain rates. By contrast, relatively little work has been carried out on the behavior of metals at hot working strain rates. Most of the latter investigations have been performed using simulative methods, such as hot torsion and hot compression, in which the friction conditions and temperature rise during deformation may differ appreciably from those existing under industrial conditions. Recently, however, Wong and Jonas1 used a scaled-down industrial process to determine the stress and temperature dependence of the strain rate during the extrusion of aluminum. In such tests, the effects of friction and adiabatic heating are closer to those produced in industrial operations. Also, with regard to the testing of materials of limited ductility such as zinc, hot compression and hot torsion do not permit the attainment of true strains as large as the deformations usually applied commercially. The present study was undertaken to investigate the extrusion behavior of Special High Grade (SHG) zinc. The detailed objectives were: 1) to establish the stress and temperature dependence of the strain rate with and without a consideration of adiabatic heating, 2) to study the pressure and temperature dependence of the ram speed, and 3) to investigate the microstruc- tural changes occurring during the deformation. The last aspect of the investigation will be covered in a separate paper. The treatment described below differs from that of Wong and Jonas in that the adiabatic temperature rise during deformation is taken into account, and the calculation of the mean equivalent strain rate is based on the redundant as well as on the homogeneous work. EXPERIMENTAL PROCEDURE Rods from two shipments of continuously cast SHG zinc* were used in the investigation. The composition *Supplied by courtesy of Cominco Ltd. range of the impurities present, as given by the supplier, was: Pb: 0.0013 to 0.0023 pct, Fe: 0.001 pct max Cd: 0.0001 to 0.0006 pct, Cu: 0.0002 to 0.0005 pct, Ti: 0.0001 pct max; thus, by balance, zinc valued from 99.9963 to 99.9966 pct. The as-received rods were machined into billets having a nominal diameter of 1.56 in. and a nominal length of 1½ in.; longer billets up to 4 in. in length, were also used to investigate special aspects. The as-machined rods were annealed at 400°C for 24 hr and slowly cooled. This treatment produced a columnar grain structure, with a grain size of about $ by 2½ cm which was appreciably larger than the as-cast one. A 150-ton, direct extrusion, vertical press was used. Ram displacement and force were recorded continuously against time. A constant flow control valve permitted the maintenance of a range of preselected ram speeds up to in. per sec. The selected speed was held constant, irrespective of the required force, as long as the load developed was below the maximum available. Strain gages were used to determine the force; the gages were calibrated before and after each testing period with a 200,000-lb capacity load cell. Further details of the experimental equipment can be found in Ref. 2. The billets were preheated for 90 min in the extrusion container, which was well insulated so as to minimize temperature gradients. This period was sufficient for the billet to reach a uniform temperature at all temperatures between 110" and 350°C. A square-shoulder die having a 0.290-in. diam central hole was used. The extrusion ratio was 30 to 1. This is equivalent to a reduction in area of 96.7 pct, an elongation of 2900 pct, and a true strain of 3.4. The ram speed was varied over two orders of magnitude from 0.0027 to 0.26 in. per sec. The ram was water-cooled during most of the tests, although some experiments were conducted with a preheated, uncooled ram. All extrusions were run without lubricant, which resulted in conditions of sticking friction. EXPERIMENTAL RESULTS Stress Dependence of the Strain Rate Neglecting Adiabatic Heating. The maximum force required to extrude is given in Table 1 for each of the five initial

Jan 1, 1970

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 S. R. Goodman, Hsun Hu

The formation of secondary - recrystallization tex-tlires in cube-textured 18-8 stain less steel (Type 304) Ilas been studied at three temperatures. Prolonged annealing at 100°&apos;C protluces a PredoninanGly (520) [OOZJ-type texture, which is related to the cube te.ture of the primary lnatrix by a rotation of approxivzately 22 deg around the [001] axis in the rolling direction. Annealing at 1200 or 1300°C facers the formation of the (123)[272/-type texture, which is related to the matrix texture by a [111] rotation of app.voxiniately 40 deg. These observations suggest that in the secondary recrystallization of cube-texlut-ed stainless steel an apparent actilation energy for growth is higher for grains related to the tncrtuix Og [111] rotations thun those reloted by [100] rotations. THE formation of secondary-recrystallization textures in cube-textured primary matrices of fcc metals has been studied widely by various investigators. For Fe-40 pct Ni alloys, Pawlek&apos; and wassermann2 reported that the orientations of secondary grains were related to the cube texture by rotations of 30 and 38 deg around [001] in the rolling direction. However, Rathenau and custers3 found that, while in one Fe-48 pct Ni alloy, most of the secondary grains were oriented with respect to the cube-textured matrix by rotations around [001] of 26.5 deg, in another alloy of a different origin, the orientations of secondary grains were related to the cube texture by rotations of approximately 35 deg around a [lll] axis. Similar orientation relationships were also observed between the secondary grains and the cube-textured primary matrices of copper.4"a No attempt was made to differentiate these two types of orientation relationships; reorientation by either a [111] or a [100] rotation was considered to be equally favored. The present investigation consisted of a study of the secondary recrystallization textures in cube-textured stainless steel. It was noted that the secondary grains formed in stainless steel were considerably smaller than those of Fe-Ni alloys or copper. This offered the advantage that the secondary recrystallization texture could be determined by the texture-goniometer technique, and a more detailed study of the textural development during the course of secondary recrystallization could be made. The effect of annealing temperature on the formation of secondary-recrystallization textures was also investigated. MATERLAL AND METHOD It was shown earlier"-" that a strong cube texture can be obtained in 18-8 stainless steels by rolling at 800°C to produce the copper-type deformation texture, followed by annealing at 800" to 1000°C for recrystallization. To improve the cube texture for the present study, a commercial-grade 18-8 stainless steel (Type 304) was rolled at 800°C first to 5 mm (0.2 in.) thick plates. Three of these plates were then stacked and welded together along the edges into a sandwich assembly. After annealing at 900°C for 20 min: the assembly was finally rolled at 800&apos;C to 90 pct reduction in thickness with reheats and end-for-end reversals after each pass. Only the central strip, which was reduced from 5.0 to 0.50 mm (0.7 in. to 0.020 in.) thick, was used. The chemical composition of the steel in weight percent was as follows: C, 0.06; Mn, 0.38: Cr, 18.71; Ni, 9.56: P, 0.011; S, 0.009; and Si, 0.39. The purpose of rolling the strip in a sandwich assembly was to prevent direct contact between the central strip and the rolls. It was observed earlier" that, when the strip was rolled at 800°C without being enclosed in a sandwich assembly, the cube texture obtained by subsequent annealing at 900" or 1000° C for recrystallization was largely confined to the central section of the strip, while most of the recrystallized grains formed in the surface section of the strip were not cube-textured. This was obviously due to the fact that the actual temperature at the strip surface during rolling, as a result of direct contact between the strip and the cold and massive rolls, was considerably lower than 800°C. By using a sandwich assembly for hot rolling, the cube texture obtained upon subsequent annealing for recrystallization was found to extend through the entire thickness of the strip. After rolling, the central strip was taken from the sandwich assembly. and cut into specimens. Prior to annealing. the specimens were etched to 0.25 mm (0.010 in.) thick. A tube furnace provided with a purified, dry argon atmosphere was used for annealing. Textures were determined by the reflection technique. using a Siemens automatic texture-goniometer and ZrOz-filtered MoKa radiation. With a time constant of 4 sec. the preferred orientation of the secondary grains could be measured satisfactorily by the integrated intensities. Both (111) and (200) reflections were measured, and corresponding pole figures were constructed according to the techniques described previously.10 The agreement between results deduced from these two reflections was excellent. RESULTS AND DISCUSSION Secondary-Recrystallization Texture due to Prolonged Annealing at 1000°C. Fig. 1 shows the primary-recrystallization texture of a specimen annealed at 1000°C for 30 min. A substantial improvement in both sharpness and intensity of the cube texture, owing to the present processing method, can be noted readily by comparing Fig. 1 with similar pole figures shown earlier in Refs. 9 and 11. Secondary recrystallization

Jan 1, 1967

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.&apos; Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1&apos; with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967

By J. C. Williams, M. J. Blackburn

Several of the decomposition processes that can occur in supersaturated phases in a Ti:11.6 wt pct Mo and a Ti:20 wt pct V alloy have been studied by transmission electron microscopy. The deformation induced "marternsitic phase" in the Ti:Mo alloy has been found to have a bcc or bct structure rather than the previously reported hexagonal structure. The morphology of&apos; the transformed region is a rather complex asserrlblage of twins, twinning occurring in one or more systems; this internal twinning has been found to occur on (112). The w phase is formed in both alloys on aging and is present in the Ti:Mo alloy after quenching. The structure of this phase has been confirmed as hexagonal in both systems, however, differences in morphology and stability are found between the two alloys. Thus in the Ti-Mo alloy the w phase has an ellipsoidal morphology with the major axis lying parallel to <111>ß or [0001]w while in the Ti-V alloy the phase forms as cubes, the cube faces lying parallel to {100}ß or {2021}w Some observations on the particle sizes, volume fraction, and composition of the w phase in the Ti-Mo alloy are listed. The mode of formation of The a phase from the (ß + w) structures is also different in the two alloys. In the Ti-Mo alloy the a phase is formed by either a cellular reaction or by the growth of isolated needles, whereas in the Ti-V alloy the a phase is nucleated at an w:ß interface and grow to consume the w phase. Some of the difjerences in behavior of the w phase are attributed to the mismatch between it and the solute enriched ß matrix in which it forms. MaNY transition elements tend to stabilize the bcc or ß-phase when added to titanium. In general two types of phase diagrams are produced, either a ß-stabilized (ß-isomorphous) system, e.g., Ti:Mo, -Ti:V, Ti:Nb, or a ß-eutectoid system, e.g., Ti:Cr, Ti:Fe, Ti:Mn. In previous papers&apos;-4 the phase transformations in the a-phase and (a + ß)-phase alloys have been described and this work has been extended to ß-stabilized systems. Specifically, transformations in the alloys Ti:20 wt pct V and Ti:11.6 wt pct Mo have been studied; in both of these alloys the ß phase is retained at room temperature when quenched from the ß-phase field. A number of phase transformations can occur in such metastable ß phases and the two alloys were chosen to include most of the transformations reported for ß-stabilized systems. We list these possible phase transformations below. Ti:11.6 Mo quenched from >780°C to retain the ß phase: a) The w phase can form on quenching.5 b) Martensite can be produced by subzero cooling or deformation. Two martensite habit planes have been reported in Ti:Mo alloys; (334)ß and (344)ß=6 c) On aging at temperatures <-550° C the w phase is formed before the a-phase.5,7 d) On aging at temperatures >550°C the a phase is formed.7 e) The martensite can be tempered. It has been reported that the a phase rather than the ß phase is precipitated during tempering.&apos; Ti:20V quenched from >660°C to retain the ß phase:9 a) At aging temperatures <260°C separation into two bcc phases occurs. b) The w-phase is produced prior to the a phase on aging at temperatures <-400°C. c) At temperatures 2400°C the a phase is formed directly. T-T-T diagrams describing the temperature and time regimes for the formation of these phases have been published7,9 for a Ti:12 pct Mo and a Ti:20 pct V alloy. We have attempted to investigate these transformations using transmission electron microscopy, however thin foils undergo a spontaneous transformation in all conditions except the equilibrium (a + ß) structure. This transformation has been reported previ0usly10,11 and we will comment on its morphology and nature in the various sections of experimental results. EXPERIMENTAL The compositions in wt pct of the two alloys investigated were: Ti:11.6 Mo, 0.100 02, 0.006 N2, 0.0015 H2 Ti:20V, 0.0574 O2, 0.0111 N2, 0.005 H2 These alloys were cold-rolled to 0.020 in. thick sheet. Specimens were heat treated in vacuum or in inert gas at temperatures >500°C and in a circulating air furnace at temperatures <500°C. Thin foils were prepared using standard techniques, described in detail previously." Dark field micrographs were obtained using high resolution technique. RESULTS Martensitic Transformation in Ti:11.6 pct Mo. Detailed study of the deformation induced martensite is not possible due to a spontaneous transformation which occurs near the edge of thin foils as shown in Fig. 1. Similar transformations have been observed in iron-" and copper-base13 alloys as well as other titanium alloys, but some observations specific to the Ti:1l.6 Mo alloy are listed below. a) The boundaries of these transformed regions are glissile and move under the influence of the electron beam during examination. b) Selected area diffraction indicates the transformed regions have the same structure as the matrix, being separated by tilt boundaries. The misori-

Jan 1, 1969