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By Colin Rawlings, Simon Pepper, Maria Karakitsiou, John Mathews, Peter Townsend, Russell Bowler, David Keeble, Christopher Darton, Scott Sadler

National Grid needs to maintain a connection between two existing electricity sub-stations (Beddington & Rowdown) in the Croydon (south London) area, and allow the replacement of two 275 kV cable circuits that are buried under roads. This is to be achieved using a single 400 kV cable circuit within a 10 km (6.25 mile) long, 3 m (9.8 ft) diameter high voltage cable tunnel which is being driven through water bearing Chalk, at depths ranging from 5 m (15 ft) to 80 m (262 ft), with four access shafts(12.5 m (41 ft) in diameter) ranging in depth from 10 m (31 ft) to 40 m (131 ft). The Chalk in this area acts as a source of public drinking water supply (PWS) and is protected by areas designated Groundwater Source Protection Zones. To minimise the groundwater risk the design and construction of the cable tunnel and shafts has paid particular attention to the construction materials used, including testing of these construction materials prior to use, developing construction methods (including the design of the Earth Pressure Balance TBM) and maintaining a groundwater monitoring & testing programme prior to and during construction to ensure the integrity of the Chalk aquifer is maintained as a drinking water source. This paper describes the tunnel &shaft design and construction in relation to these particular groundwater environmental issues which set new precedents for tunnel assessment, design and construction requirements in the United Kingdom.

Jan 1, 2007

By Chris D. Thompson

In Southern Ontario, Canada, piles are frequently driven through competent clayey soils to obtain end bearing on extremely dense till or bedrock. One reason for this is the difficulty at assessing the adhesion of the clayey soils. This is illustrated by texts, such as the Canadian Foundation Engineering Manual, which is the standard of practice in Canada, that indicate that theoretical analysis of the adhesion values of such soils are unreliable. In this paper, the results of high strain dynamic testing have been used to estimate the shaft resistance of 11 closed end pipe piles driven in overconsolidated very stiff to hard clayey tills at four sites by means of the CAPWAP wave equation analysis. More than twenty-five years of experience with bearing capacity predictions by such means have developed considerable confidence in its accuracy. The results were found to correlate reasonably with the average Standard Penetration Resistances of the clays at the sites. There was a linear relationship between an adhesion of 64 kPa at 20 blows per 300 mm and 192 kPa at 60 blows per 300 mm. At one site, 6 piles were tested and found to have a wide range of Standard Penetration Resistance and estimated adhesion in the same stratum. While there was significant scatter of the results, piles would have been safe at design loads obtained from the relationships established by the analysis carried out for this paper after applying appropriate factors of safety.

Jan 1, 2002

By E. M. Cameron

Reconnaissance radiometric and geochemical data have been obtained for an area on the western shore of Wollaston Lake that includes the Rabbit Lake uranium deposit. The study area is extensively drift cover ed. The geochemical data were obtained by analysis of center-lake sediments and surface waters for a variety of elements and other constituents. The airborne radiometric data comprise measurements of eU, eTh and K obtained with a .50,000-cc NaI (Tl) detector at a mean terrain clearance of 120 m and 5-km flight-line spacing. Uranium in lake sediments and uranium in waters are the most effective geochemical indicators of uranium mineralization; the other elements measured are not notably anomalous. A sample site density of one per 1 8 km 2 is more than adequate for identification of the mineralized area. Because many water samples contain close to or below the current analytical detection limit of 0.05 ppb U, the use of sediments is generally favoured. for broad-scale reconnaissance in the region. Uranium in these lake sediments appears to be little influenced by variations in the organic or iron and manganese content. The most effective radiometric indicator of the mineralization is the eU/eTh ratio. This parameter is less influenced by environmental variation on the ground beneath the flight line than eU alone . The eTh/K ratio is anomalous under the Athabasca Formation unconformity where, in places, the uranium mineralization is localized.

Jan 1, 1977

By J. P. Morris

A diphenyl ether calorimeter for measuring high-temperature heat contents of ferrous alloys and iron-and steelmaking slags was constructed and calibrated with specimens of molybdenum, alumina, and platinum that were heated to temperatures ranging from 1,720° to 1,875° K. The standard deviation of the calibration measurements was 0.37 percent. By measurements of the enthalpy of delta and liquid iron, the heat of fusion of iron was found to be 3,298 ±100 cal per mole.

Jan 1, 1966

By E. Krause

The oxidation of Fe(II) with S(IV) and oxygen can be used advantageously in leaching systems requiring both Fe(III) and sulfuric acid; e.g., heap leaching of sulfide-containing ores or concentrates. The oxidation of Fe(II) with SO2/air is several orders of magnitude faster than with air alone; rates of up to ?20 g/L'h were observed at 25°C. The reaction proceeds via an intermediate orange-red mixed-valence Fe(II)/Fe(III) sulfite complex, which is present at an essentially constant concentration throughout most of the oxidation process. The oxidation rate of Fe(II) is approximated by the formula -d[Fe(II)]/dt = k [S(IV)] [02]0'3. The concentration of the mixed-valence complex, and thus the iron oxidation rate, decreases with increasing acidity. Certain impurities, such as SCN- and thiourea, negatively affect the rate. The oxidation reaction 2Fe2 + SO2 + 02 4 2Fe3+ + S042- is accompanied by the side reaction H20 + SO2 + 1/202 4 H2SO4. The side reaction becomes particularly important at low temperatures and whenever the oxygen mass transfer is insufficient with respect to the rate of addition of S(IV). Thus, effective oxygen mass transfer is essential for achieving high oxidation rates with minimal acid formation. The activation energy was estimated as 141 kJ/mol over the temperature range 10-35°C.

Jan 1, 2006

By John B. Wright

This paper describes laboratory techniques and subsequent results of Bureau of Mines research to produce chlorination-grade feedstock from an abundant, low-grade, domestic, rock ilmenite ore. The research is part of the Bureau-effort to devise technology that may help decrease U.S. dependence on imported raw materials. A rock ilmenite containing about 46 wt pct Ti02 was smelted in an electric arc furnace with coke, woodchips, and Na2C03 to separate most of the iron as pig iron and to form a low-iron, titanium-enriched slag. The slag was ground, pelletized, oxidized, and then sulfated with mixtures of SO2 and air in a continuous 4.5- to 9.1- kg/h apparatus at 1023 to 1223 K. The sulfated slag, containing 60 to 65 pct TiO2, was reground and leached in water at ambient temperature to decrease the combined levels of the troublesome Ca, Mg, and Mn impurities from 7.0 to 1.7 wt pct. At levels of more than 3 wt pct, these impurities contribute to operating and disposal problems, The final product was upgraded to about 84 wt pct TiO2. This material potentially is suitable for chlorination in a fluidized-bed reactor. The most favorable results were achieved with leached slag sulfated at a feedrate of 4.5 kg/h and at temperatures of 1073 to 1123 K.

Jan 1, 1984

By Rongjie Kong, Shiwei Wang, Dongjiao Gui

Metal cations have significant effects on the flotation of coal and minerals. In this study, the effects of monovalent cations ( Na+ and K+) on the flotation of low-rank coal (LRC) were investigated using flotation and particle–bubble attachment experiments and through X-ray photoelectron spectroscopy (XPS) and molecular dynamics simulations. Oleic acid (OA), methyl linoleate (ML), hexadecyltrimethylammonium chloride (CTAC), ricinoleic acid (RA), and kerosene were used as flotation collectors. The flotation experiments revealed that the flotation yields of LRC improved when OA, ML, RA, CTAC, and kerosene were used in pure deionized water. However, flotation was suppressed for these collectors in the presence of K+ and Na+ ions. In contrast, when using CTAC, the flotation yield increased in the presence of these ions. Specifically, the flotation yield increased from 41.24 to 87.03% when 2.0 kg/t CTAC was used in 10 mmol/L NaCl solution. Particle–bubble adhesion experiments and XPS revealed that the hydrophilic groups of CTAC were adsorbed on the LRC surfaces by electrostatic forces, whereas the oxygen-containing functional groups of OA, ML, and RA formed hydrogen bonds with the LRC surface in pure water. Finally, the simulating result revealed that the hydrophobic ends of the OA, ML, and RA collectors hinder the flotation of LRC by adsorbing monovalent cations, whereas the adsorption of monovalent cations on the hydrophobic end of the cationic surfactant (CTAC) promotes flotation via strong electrostatic interactions.

Jan 31, 2024

By Drummond Earley III

The U.S. Bureau of Mines is currently conducting laboratory experiments to study the reactions occurring during in situ leaching of oxide copper ores hosted by biotite-poor granite and biotite-rich granite porphyry. Detailed pre-leach and post-leach petrographic examinations of the rock samples are combined with the leach solution chemistry resulting from core leaching experiments to enable an evaluation of the various reactions which are responsible for the observed fluid chemistry. The information resulting from these laboratory studies is being utilized to support the design of the Bureau's ongoing field research project at the Santa Cruz deposit near Casa Grande, AZ. Atacamite and chrysocolla are the primary copper minerals present in this deposit, and both are readily soluble in the dilute 5% sulfuric acid solutions used in these experiments. In addition to the dissolution of copper minerals, biotite dissolution also occurs during the experiments, contributing K, Mg, Fe, and Al to the leach solution. The biotite dissolution appears to be non-stoichiometric, as it is progressively altered to vermiculite and finally, amorphous silica. While K, Mg, and Fe concentrations in solution steadily increase with time, Al quickly reaches a maximum, and then remains relatively constant for the remainder of the experiment. This suggests that Al saturation is achieved, and this Is supported by the presence of precipitated Al sulfate and aluminosillcate clay mineralization in the post-leach rock samples.

Jan 1, 1990

By H. Razavizadeh

The recovery of copper from oxide ores containing from 2% to 4.1% acid-soluble copper from the Sarcheshmeh mine in Kerman province of Iran was investigated by agitation leaching in sulfuric acid media. Quartz, as a major constituent, and malachite, as the major copper mineral, were identified in the ore by X-ray diffraction (XRD) and microscopic studies. A series of leaching experiments on the ore was performed over a concentration range of 10 to 20 g/L and temperatures from 15° to 50°C for a maximum of 3 hours. An initial high dissolution of copper was followed by a very slow reaction. By increasing acid concentration and temperature, the dissolution rate of copper was accelerated. However, by increasing acid concentration, the acid consumption of ores was also increased. Surface morphology of solid residues at various leaching times was examined with a scanning electron microscope (SEM). All SEM micrographs of the partially reacted particles displayed a needle structure. The kinetic studies showed that the malachite dissolution rate could be modeled in two stages. About 85% of the malachite dissolution occurred in Stage 1, while the remaining 15% occurred in Stage 2. The data obtained for the leaching kinetics indicate that the dissolution for Stage 1 was a diffusion-controlled reaction with an activation energy of about 20.6 kJ/mole, and the dissolution for the Stag 2 was a chemical-controlled reaction with an activation energy of about 87.6 kJ/mole.

Jan 1, 2008

By Valery Kaplan

Sulfur emission in the form of SO2 in flue gases is one of the most serious atmospheric pollutants associated with coal combustion and non-ferrous metals production. The carbonate eutectic method for removing SO2 from flue gases at 723–923 K was initially proposed in the 1970s but despite its great efficiency (SO2 concentration in the flue gas after purification reached 0.003 volume %), it could not be implemented by industry due to the complexity of the carbonate melt regeneration stage. Earlier we proposed a method suited to coal-firing power stations where the melt was regenerated using CO as a reducing agent. However, most metallurgical plants do not use coal and therefore lack a large source of CO. Here we propose a method for removing sulfur from the carbonate eutectic melt by purging it with natural gas or a natural gas/air mixture, which are available in the vast majority of metallurgical plants. This reaction leads to the reduction of sulfate to H2S gas that leaves the melt. The experiments we conducted show that nearly complete sulfur removal from the melt is possible at 823 K and that the reaction rate is sufficiently high for a large scale process. One can foresee that this carbonate melt-based SO2 removal technique may become a practical and economically attractive method for limiting sulfur emission to the atmosphere from non-ferrous metallurgical processing plants.

By Yanhui Liu, Xuewei Lv, Chenguang Bai

A thermodynamic model for determining the surface tension of molten slag by considering the surface tension and molar volume of the pure oxide component, and their ionic radii was extended to the slag bearing high TiO2 (varying from 80 to 67%) at 1973 K. The iso-surface tension curves for the FeO-TiO2-Ti2O3 ternary system at 1973 K are almost parallel to the FeOTi2O3 line. TiO2 plays a role of surface-active solute, and its surface-active effect is attenuating with increasing the TiO2 content. The iso-surface tension curve shifts away from the TiO2 corner, indicating that the surface tension of the ternary slag decreases along with the addition of SiO2. The reasons include the addition of SiO2 with lower surface tension and the decrease of the total ion moment at the surface. Both CaO and MgO can bring about that the iso-surface tension curve shifts towards the TiO2 corner, indicating that the surface tension of the ternary slag increases along with the addition of CaO or MgO. CaO has a more pronounced effect on increasing the surface tension of the ternary slag than MgO at an equimolar amount addition. The increase of the surface tension results from both the compositional change and the variation of the slag structure.

Jan 1, 2015

By Dinesh Goyal

Industrial fly ash from (electro static precipitator) was mixed with soil at different levels on v/v basis for raising of pulpwood tree species. In field trials conducted on degraded soils increase in the plant growth of Eucalyptus tereticornis, Acacia auriculiformis and Casuarina equisetifolia by 10 %, was observed during the initial six months after plantation at 18-24% (v/v) fly ash concentration which was at par with chemical fertilizer treatment. Level of As, Se and Mo in flyash was 6.2, 3.6 and 4.0 ppm respectively. The radioactivity analyses 40K, soil and 28 fly ash showed that the activity levels of gamma emitting radionuclides K, Ra, Ac were within the permissible limits and mixing of fly ash with soil at tested concentration would have no deleterious effects. Available Co, Cr, Ni and Cd in rhizospheric soils were below detection limit. Fly ash at 10-20 % level (v/v) was also found to be a good potting mix material in forestry nurseries in terms of improving biomass production by 20 %, when tested in nursery seedlings of Eucalyptus tereticornis. Nursery addition of fly ash in soil decreased soil dehydrogenase activity and the soil bacterial population was negatively affected. These results indicate that use of fly ash in forestry sector involving nursery and plantations as a soil amendment agent upto 10-20 % v/v is a gainful utilisation of fly ash.

Jan 1, 2002

By Jochen Petersen, Caroline Muzawazi

The technical feasibility of ammonia leaching of PGM bearing Platreef flotation concentrates was investigated as an alternative method for the recovery of base metals prior to precious metal recovery. The composition of the concentrates includes 2.02% Cu and 3.17% Ni, and the major base metal minerals are chalcopyrite and pentlandite. Optimal leaching conditions were initially established in shake flask experiments to be a solution containing 4 M NH4OH, 4 M (NH4)2CO3 and a pH range between 9 and 10. These were used as base case conditions in column and batch stirred tank reactor tests, where the effects of total ammonia concentration and operating temperature were explored further. At optimal conditions nearly 100% Cu and Ni extraction were obtained in the batch stirred tank reactor, and 95% Cu and 60% Ni extraction was obtained in columns. The activation energy for chalcopyrite and pentlandite was 36 kJ/mol and 16 kJ/mol, respectively, in both reactors, indicating different reaction pathways for the two minerals. Gas-liquid mass transfer appears to be the limiting reaction step in columns much more than in tanks, and the degree of ammonia loss to air is significant. This initial test work indicates the feasibility of using ammonia leaching for this and similar materials as an alternative route to conventional smelting and refining prior to PGM recovery, but a number of technical challenges still need to be overcome.

Jan 1, 2014

By M. Mortada

Nonsteady-state flow of slightly compressible liquids in porous media of non-uniform properties has been the subject of a number of recent studies. Most of these studies considered one-dimensional flow in systems with cylindrical geometry and with the properties of the porous medium varying with radial distance only. A. Houpeurt' studied the problem in its general form by examining the solutions of the differential equation, In Eq. 1, the permeability k and the porosity + are arbitrary functions of radial distance. Houpeurt concluded that, except for special forms of the functions k and the problem is not well suited for mathematical treatment, but lends itself to high-speed digital computation. Carslaw and Jaeger' discussed the solution of Eq. 1 for the case in which the permeability varies as a power of the radial distance. P. Albert3 studied analytically the pseudo steady-state solutions in systems of finite radial extent and non-uniform properties. He also obtained some numerical solutions for nonsteady-state flow using a high-speed computer. William Hurst4 examined the interference pressure drop due to a point sink located in an infinite system consisting of two permeability regions in series. In this case, the permeability changed at a radial distance r from the point sink. INTERFERENCE BETWEEN OIL FIELDS IN A NON-UNIFORM AQUIFER The interference pressure drop for oil fields located in an extensive aquifer of uniform properties is discussed in a number of places in the literature. This work considers the interference pressure drop for oil fields located in a non-uniform extensive aquifer comprising two regions of different properties as shown in Fig. 1. Region I of the aquifer extends from which is the radius of Oil Field A, to ar,,, where a>1. It has permeability k,, porosity +, and effective compressibility c,. Oil Field B is located in Region II which extends from ar, to infinity and has different properties from those of Region I, but the same formation thickness h. Region II has permeability k2, porosity and effective compressibility c2. The choice of this type of aquifer should not imply that it is of frequent occurrence. It is chosen primarily to illustrate the effects of non-uniform aquifer properties on oilfield interference. It is of interest to point out that a non-uniform radial aquifer in which both the permeability and the porosity are inversely proportional to the radial distance can be treated in a manner similar to a linear aquifer of uniform properties. The situation where only the permeability varies as the inverse of the radial distance is also amenable to analytical treatment. Both aquifers behave quite differently from a radial aquifer with uniform properties so far as the water influx and the interference pressure drop are concerned. METHOD OF SOLUTION The expression for the interference pressure drop in Oil Field B due to a constant rate of water influx in Oil Field A is developed in the Appendix. This is accomplished by the simultaneous solution of two partial differential equations describing the pressure in Regions I and 11. The two differential equations are solved subject to the following conditions: (1) at r,, the pressure gradient is constant; (2) at ar the pressure and

By Milton E. Wadsworth, John N. Ong, W. Martin Fassell

The temperature and oxygen concentration dependence on the reaction of sphalerite in oxygen at pressures from 6 to 640 mm Hg have been investigated in the temperature range 700° to 870°C. Sphalerite has been found to oxidize linearly over this entire temperature and pressure range. At higher rates, considerable self-heating was observed. The dependence of the oxidation rate on the oxygen concentration may be expressed by: Rate = k' where k' is the specific rate constant and 0 = K1[O2]/(1 + KI[O2]), where K1 is the equilibrium rate constant for the adsorption of oxygen on sphalerite. Values of the activation energy and the enthalpy of adsorption were found to be 60.3 and —59.6 kcal per mol, respectively. Data have been presented that indicate conditions under which either a sulphatizing or an oxidizing roast may be obtained. ROASTING processes have been employed in the metallurgy of a great number of basic metals in use today. Until recently, however, little attempt has been made to deduce the fundamental mechanism by which oxidation takes place. Structural changes upon oxidation have been investigated1 = and thorough work has been performed with regard to the reaction products and the thermodynamics of the oxidation reactions. The objective of this investigation was to determine the rate of oxidation of sphalerite and to apply the absolute reaction rate theory in the theoretilcal interpretation of the experimental results." "O Description of Apparatus The apparatus contains the following features: 1—a furnace with gas system, 2—an autographic weighing system, and 3—a temperature control system. Furnace With Gas System—The furnace was mounted by a yoke on each end and was free to travel up and down on steel guide rods, permitting the introduction and removal of samples from the apparatus with minimum difficulty. The furnace was heated by three sections of Kanthal wire wound externally on a zirconia tube and insulated with Fiber-frax. Pure gases or mixtures of gases were introduced into the lower end of the furnace through two flowmeters, a mixing chamber, and a gas-tight sparger, Fig. 1. The gaseous products of the reaction and the unused gases were prevented from escaping to the atmosphere by maintaining a small negative pressure on the system. This procedure permitted air from the outside to enter through the small an-nulus around the quartz suspension fiber and prevented the escape of the internal gases. Autographic Weighing System—The autographic weighing system consisted of an adapted gold balance, a photoelectric circuit, and a weight recorder, Fig. 2. The sample was suspended from one end of the balance beam by means of a platinum chain outside the furnace and a long thin quartz fiber on the inside of the furnace. On the other end of the balance beam, the necessary weights were added to counterbalance the sample. In addition, a calibrated chain was added to the balance which was linked directly to the weight recording unit. Control was effected by means of a photoelectric circuit." A parallel beam of light from a strong source was directed onto a small front-surfaced aluminum mirror mounted in the middle of the balance beam and then to a front-surfaced mirror mounted on the ceiling of the room. The beam was then reflected onto a front-surfaced right prism at a distance of 9 ft from the balance

Jan 1, 1957

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith's graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970

By E. R. Buchanan, R. E. Reed-Hill, F. W. Caldwell

Poly crystalline zirconium tensile specimens containing a sizable fraction of grains unfavorably oriented for slip were deformed at 77°K to strains as high as 9 pct. The contributions of the various twinning modes to the observed strain were deter~nlned quantitatively using measured twin volume fractions and Schrnid orientation factors. The results indicate that at very small strains twinning can account for almost all of the observed strain. At higher strains slip becomes the dominant means of deformation. The most significant form of twinning was {1121}. PLASTIC deformation in polycrystalline aggregates is poorly understood even today. This is primarily because slip cannot be easily observed or studied in the interior of a metal. On the other hand, twinning can be discerned inside a specimen after deformation. Twinning studies can therefore often yield quantitative information about polycrystalline deformation not otherwise obtainable. This investigation uses the above aspect of twinning in determining the contributions of twinning to the strain during tensile deformation at a cryogenic temperature (77°K). Polycrystalline zirconium was used as the object of study. There are several reasons why this information should be of value. In contrast to many metals, both the strength and ductility of zirconium increase with a corresponding decrease in temperature. This may be related to the fact that twinning becomes more profuse and complex with decreasing temperature. Secondly, it has been discovered that certain room-temperature properties of zirconium can be greatly improved by about 1 pct prestrain at 77°K. These include an increase in tensile elongation in critical directions by over 50 pctl and a large mechanical hysteresis effect.2 Both effects are believed to be related to twins formed by prestraining: plastic twin-boundary movements accounting for the increased ductility, and anelastic twin-boundary movements for the internal friction. Thirdly, hexagonal metals which twin primarily on only the (1012) mode (such as beryllium, zinc, and magnesium), unlike zirconium, are very limited in ductility at cryogenic temperatures. Therefore, the significance of the various types of twinning in zirconium at cryogenic temperatures is of more than academic interest. Three twinning mechanism-s have beenobserved in quantity at WOK, {1012), {1121), and {1122). Each must be considered as a unique deformation mechanism because of their markedly different twinning shears and basically different angles between twinning and basal planes, as shown in Table I. It is therefore necessary to separately consider the role of each of these twins during plastic deformation at 77°K. Fortunately, each twin possesses unique morphological features which makes its identification possible on a properly prepared metallographic section. The use of the polarized microscope3 can also greatly aid in identification of the various forms of twins. EXPERIMENTAL PROCEDURE Arc-melted sponge zirconium plate, previously describedY4 was machined into 1/8 by 1 1/4 in. threaded-end, round tensile test specimens. These specimens were deformed to the desired strains in a liquid-nitrogen cryostat mounted in an Instron testing machine. The tensile axis was the transverse plate direction. This specimen direction resulted in large numbers of grains in orientations unfavorable for deformation by prism or basal slip. Deformed specimens were sectioned, mounted in epoxy cold-mount resin, ground on metallographic papers, electropolished, and anodized to provide surfaces sensitive to polarized light. Standard quantitative metallographic procedures5

Jan 1, 1965

By D. Mills, G. B. Craig

The defortnaliotz of zirconicltt single crystals conlaining osygen in the range 740 to 6800 atom parts per nilllion was esanined oc7er the range 77" to 950°K. An anctlsis of the dqfarmaliotz parameters leads to the cotcllsiotr that the rale -cotzfrolling thermally activated dqivr,irrtion process oe-r /he range 77" to 560°K is oc.crco,ling osvgen alotns. A thermally actitaled defor,ilntion process is not found between 600" and 800", but does occur aboz%e 800°K. THE present investigation was undertaken to measure the effects of controlled amounts of oxygen on the deformation parameters of a zirconium single crystals over the temperature range 77" to 950°K and to determine the rate-controlling mechanisms. Although there is no doubt that the mechanical properties of the group IV metals, titanium, zirconium, and hafnium, are strongly influenced by the interstitial impurities oxygen, nitrogen, carbon, and hydrogen, there are many conflicting theories as to the role played by the interstitials during the deformation proess.'- There is general agreement that the mechanisms which control plastic flow in a metal impose characteristic values on such parameters as the flow stress and its temperature dependence, the activation volume, and the activation energies. These parameters will be used to analyze the deformation mechanisms. eltham,' Sargent,16 and ibbs' have shown that the stress relaxation technique allows the activation volume characteristic of the deformation process to be found during the course of a simple tension test. In many cases it is found that the relaxation of stress is logarithmic with time and obeys a relationship of the following form: T-T = AT =S logl0(qt + C) [I] where t, is the shear stress at the start of the relaxation test, t is the shear stress at time t, and S. q, and C are experimental constants, and S is the strain rate sensitivity of the stress t as shown in the appendix. The slope found from a semilogarithmic plot of At vs time is approximately equal to S. The activation volume u, association with the deformation process, is found from the following relationship: The theoretical treatment of thermally activated plastic flow due to schoeck18 shows that the activation volume when combined with the temperature dependence of the flow stress gives the activation energy for the process according to equations: seegerZ3 considers that the flow stress at lower temperatures ld is composed of two parts such that Tapplied = tinternal + Teffective , where Teffective 3 ff , is the stress necessary to overcome the local obstacles to deformation and Tinternal, ri, is the stress necessary to overcome the long-range elastic stress field of dislocations on other planes. ri is considered to be largely elastic in origin and can be estimated from the stress value at the temperature independent portion of the flow stress-temperature curve. EXPERIMENTAL The crystal bar zirconium used in this investigation was supplied by Wah Chang Corp. whose certified analysis gave the following impurity contents in parts per million by weight: oxygen, 150; nitrogen, 10; iron, 180. All others were less than 100 ppm. The oxygen and iron contents were confirmed by neutron activation and chemical analyses, respectively. Single crystals were grown in an electron beam furnace according to the method of Wilson and Pickle-simer'' and ills.'' The orientation of the crystals was such that the specimen axes were located in the lower third of the standard section of the basal plane stereographic projection for zirconium. This orienta-

Jan 1, 1969

By S. F. Frederick, G. F. Pittinato

The deformation mechanisms operating in Ti-5Al-2.5Sn at 20°K under uniaxial and biaxial stress fields were determined by using both optical and electron microscopy. In the uniaxially stressed specimens, de-fu~rnation twins were found only in the immediate vicinity of the fracture. Twinning was, however, established as a deformation mechanism under biaxial stress conditions. The same slip systems were opera-tiz,e under both uniaxial and biaxial stress. Prismatic slip was identified as the major slip syslem; however, basal and first-order pyramidal slip also occurred, but to a lesser degree. The interaction of moving dis-locations on intersecting slip planes resulted in the formation of jogs and dipoles. Hexagonal dislocation networks were formed only under biaxial stress conditions. A discussion is given on the formation of hexagonal dislocation networks. IT has been shown that titanium alloys can exhibit unusually high strengths when tested in a biaxial stress field.'-" The high biaxial strengths are a consequence of a strong basal plane sheet texture which results in distinctly anisotropic flow properties. This texture strengthening appears to decrease with decreasing temperature2 and would seem to indicate a change in deformation modes. For example, in a uniaxial tensile test, Ti-5A1-2.5Sn yields isotropically at 20°K but is strongly anisotropic at room temperature. The increase in biaxial ultimate over uniaxial strength at 20°K is also much less than at room temperature. It is known that titanium car] form deformation twins more readily at cryogenic temperatures than at room temperature.4 Since the formation of deformation twins will reduce the degree of basal texture in sheet material,' an accompanying decrease in texture strengthening would be expected. To investigate more fully the nature of texture strengthening at cryogenic temperatures, the deformation modes of Ti-5A1-2.5Sn tested in uniaxial and 1:1 biaxial tension at 20°K were studied by optical and electron transmission microscopy. EXPERIMENTAL PROCEDURE The uniaxial and biaxial stress test specimens were prepared from 0.020-in. thick sheets of Ti-5A1-2.5Sn ELI having the composition shown in Table I. Uniaxial stress conditions were obtained by using flat tensile specimens machined from the sheet material. The longitudinal axis of the tensile specimens was aligned perpendicular to the rolling direction of the sheet. Tile biaxial test specimens were prepared by rolling precut, 19-in.-lengths of sheet into 4-in.-diam cyl- inders. Following longitudinal butt welding, the cylinders were stress relieved at 1000°F for 4 hr. A 9-in. sq "window" was then chemically milled into each cylinder's surface reducing the wall thickness in the milled area to approximately 0.006 in. The testing procedure consisted of pressurizing the cylinders while simultaneously applying a tensile load. Using this technique, a 1:l axial to hoop stress was obtained. Complete details of the specimen and testing procedures are given in Refs. 1 and 2. The biaxial and uniaxial stress specimens were all tested in liquid hydrogen. Specimens for electron transmission microscopy were prepared by first chemically milling to a thickness of about 0.001 in. followed by electrolytic polishing to electron transmission thickness. The chemical milling solution, consisting of 800 ml of water,

Jan 1, 1970

By R. G. Charles, E. A. Gulbransen, S. Barnartt

KINETICS of the reaction of zirconium with pure oxygen at elevated temperatures have been studied by several workers for periods of time up to 6 hr.1-1 In two cases,3-4 . the experimental values of oxygen uptake, w, as a function of time, t, were best fitted to the parabolic rate law w2 = kPt + constant. In others,3,4 the cubic rate law w3 = kot + constant, showed better agreement. The most recent data of Gulbransen and Andrew4 indicate that the choice between the parabolic and cubic laws for empirical representation of the data will often be arbitrary. This is particularly true if the first few minutes of the reaction with a clean zirconium surface is attributed to a different oxidation mechanism, for deviations from either rate law were found primarily during the initial period. Thus, the kinetics of this reaction have been too uncertain to permit safe extrapolation to oxidation periods of practical interest (many hundreds of hours). The data to be described are of interest, for they indicate that the cubic rate law applies over long oxidation times. The reaction of zirconium with oxygen at 1 atm pressure was followed at 350" and 450°C for 500 and 200 hr, respectively. Abraded test specimens of pure zirconium sheet' 3.0 X 2.0 X 0.012 cm in size were oxidized by the procedure previously described,3 which included periodic cooling to room temperature for weighing. The surfaces were polished to a 4/0 finish using polishing paper wet with kerosene, then wiped with petroleum ether and washed in redistilled acetone. Fig. 1 shows plots of log ? vs log t. Each curve represents the average of duplicate measurements, and deviations from the average were generally less than 3 pet. The cubic rate law (slope = 1/3) is closely followed. The rate constants, 5.2, x 10 -6 and 2.4, X 10- (mg cm-2)3 per hr at 350" and 450 oC, respectively, are plotted as log k, vs 1/T in Fig. 2, together with cubic constants calculated from the data of Gulbransen and Andrew4 for abraded specimens from the same lot of zirconium. Their data refer to runs of 6-hr duration at a pressure of 0.1 atm 0 and under conditions of uninterrupted heating. In spite of these differences, the latter data yield a straight line which appears to apply equally well to the new extended time data. The energy of activation for the oxidation process, calculated from the slope of this line, i.s 38 keal per mole. This may be compared with the value of 47 keal per mole found by Belle and Mallett3 at higher temperatures. It may be concluded tentatively that extrapolation of short-term oxidation data for zirconium to obtain the long-term behavior is best done through the cubic equation ?3 = kpt + constant. References ' E. A. Gulbransen and K. F. Andrew: AIME Trans., 1949, vol. 185, p. A.515; JouRNal OF Metals, August 1949. 'D.p. Cubicciotti Journal Amer Chemical August1949.Soc., 1950, Vol. 72, P. 3 V. Belle and M. W. Mallett: Joulnal Electro chemical Soc., 1954, ' E. A. Gulbransen 339.and K. F. Andrew: Oxidation of Zirconium Between 400" Gulbransenand 800'C.and AIME Trarzs.. 1957, vol. 209, p. 394; JOUR-Nal of Metals, April 1957. IS Barnartt, B G. Charles, and E. A. Gulbransen: Oxidation of 50 weight pet uranium-zirconium alloy, Journul Electrochemical SOC., 1957, vol. 104, p. 218.

Jan 1, 1959