Search Documents

By D. J. Schmatz, H. I. Aaronson, H. A. Domian

Diffusion kinetics in disordered hcp Cd-Mg alloys have been investigated by means of the Kirkendall effect and concentration-penetration curves determined with an electron-microprobe analyzer. Self-diffusion coefficients of both species were determined at the three marker compositions obtained, averaging 27.6, 46. 7, and 78.1 at. pct Mg, by means of the Darken analysis. These coefficients were then corrected for the unequal and concentration-dependent partial molar volumes of the two elements with the Balluffi analysis, and for the vacancy flux effect by the Manning analysis. The latter correction reduced the Balluffi correction produced larger changes in the self-diffusiv-ities; neither, however, produced statistically significant changes in the Do's or the H'S. The most striking result of this investigation is that at all three compositions and at all temperatures studied both the uncorrected and corrected self-difjusivities of magnesium are higher than those of cadmium. The Cd-Mg system is the first one found in which the higher melting, lower vapor pressure element diffuses more rapidly. Both an empirical correlation due to Toth and Searcy and considerations of the atomic mechanism of diffusion indicate that this anomaly is probably due to a comparatively low value of the activation energy required for a magnesium atom and a vacancy to exchange sites, perhaps occasioned by the higher compressibility of magnesium atoms. KIRKENDALL effect studies have been previously reported for only two hcp solid solutions: the E phase of the Zn-Cu system1 and the a phase of the Cd-Hg system.' In neither investigation were the marker-movement studies supplemented with the concentration-penetration curve determinations necessary to evaluate self-diffusivities by means of the atano and the Darken analyses. The present program was undertaken to obtain both types of data on a hexagonal solid solution in order to provide more detailed information relevant to the mechanism of diffusion in this type of lattice. The Cd-Mg system was chosen for this study because the disordered solid solution extends across the entire phase diagram at temperatures above 253"c5 and the substantial difference in the melting points of the component pure metals promised that marker movements would occur at reasonably rapid rates should the diffusivities of the two species be as unequal as might be anticipated. The experimental convenience of the relatively low melting points of cad-miun and magnesium and the availability of extensive and accurate activity data6 (required for application of the Darken analysis) were additional reasons for selecting this alloy system. Since the anisotropy of diffusion is not large in either pure cadmium7 or pure magnesium,' the diffusion couples were prepared from polycrystalline components. The presence of a well-defined texture in the couples—the c axis of individual crystals tended to be normal to the diffusion direction— however, provides a fair degree of crystallographic definition to the data obtained. The principal (and entirely unexpected) finding of this investigation, that magnesium, the high-melting low-vapor pressure element, diffuses more rapidly than cadmium, in contradiction to a broad range of results in fcc and bcc alloys, as well as in the previously studied hcp alloys,172 makes the self-diffusivity determinations of immediate interest in understanding the origin of this anomalous result. EXPERIMENTAL PROCEDURE The cadmium (Belmont Smelting and Refining Co.) and magnesium (Dow Chemical Co.) used in this study were both of 99.99 pct purity. Alloys containing 51.0 and 65.6 at. pct Mg were prepared from these materials by melting under a MgC12-base flux in a high-purity graphite crucible. These alloys were subsequently hot-worked and then homogenized in a helium atmosphere at temperatures close to their solidus points. Sandwich-type diffusion couples of the type g/d/g were prepared from the pure metals by solid-state diffusion. Two-piece alloy couples of Mg/65.5 at. pct Mg (Mg/gCd) and Cd/51.0 at. pct Mg (Cd/CdMg) were welded by a liquation technique. The individual components of both types of couple were initially cylinders 1.27 cm in diam and in length; the ends of these cylinders were machined accurately flat and parallel. For both welding techniques, the pure cadmium cylinders and the alloys were chemically polished in a mixture of 40 pct ethyl alcohol, 40 pct hydrogen peroxide (30 pct conc), and 20 pct nitric acid,g while those of pure magnesium were polished in a solution of 10 pct nitric acid in ethyl alcohol.' Immediately afterwards, both metals were rinsed in freshly distilled acetone, and then in similarly purified methanol.' The Mg/Cd/g couples were assembled in a carefully cleaned stainless-steel welding fixture, in which a screw operating through a self-centering arrangement permitted a controlled pressure to be exerted upon a couple prior to welding.'' Tungsten marker wires 0.005 cm in diam were placed at the d:g interfaces of some of these couples, and imbedded in the couples during the application of pressure. As soon as a couple had been assembled, the welding fixture was inserted into a Pyrex capsule containing a packet of zirconium chips at each end. The capsule

Jan 1, 1967

By T. F. Bower, M. C. Flemings

Results are reported of a study of surface dendrilic structure of an Al- Cu alloy solidified against a chill wall. Most primary and secondary "arms " in the surface dendritic structure are arranged orthogonally, giving the impression of strong preferred orientalion on the surface. However, no such preferred orientation exists and it is therefore evident the arms do not represent (100) directions. The primary arms are shown to be interseclions of a (100) plane wilh the chill plane, or, equally often. the projeclion of a (100) direction on the chill plane. Secondary dendrite arms are usually within a few degrees of 90 deg to the primary arm, independent of grain orientalion. Prirary, secondary, and higher-order surface dendrite arms almost always represenl intersections of (100) platzes with the chill surace, or pvojections of (100) direclions. Growlh of secondary arms is favored on the side of the primary arm where a (100) direclion points toward the chill surfAce a1 a Lou, angle. Surface dendrile arms are often observed to be bent. In these cases, the crystal lallice changes orientation; bending is concave to the chill surface. In a previous paper,' a technique was discussed whereby large grains can be obtained at a chill surface. The technique used involves quickly drawing superheated liquid A1-4.5 pct Cu alloy into a thin copper mold, so that the mold is full well before solidification begins. The chill surfaces employed are polished copper blocks coated with amorphous carbon. Shrinkage during solidification between dendrite arms and grains delineates both, without the need for polishing or etching of the cast surface. The grain structure of the chill surface was discussed in a previous paper;' in this paper, the dendrite arms within each grain are examined. Previous work on surface dendrites includes that of Edmunds, who studied the development of preferred orientation in zinc, cadmium, and magnesium.' In zinc and cadmium, he found that the surface region has a (0001) texture (parallel to the chill surface). Walton and Chalmers reasoned that, since the fast growth (1010) directions are in the basal plane, nuclei which have this plane parallel to the mold wall would produce larger grains than nuclei with other orientations. Hence, the texture observed is as expected.3 The same authors, in measurements on aluminum ingots, found no preferred orientation at the mold wall. However, the X-ray technique they used measured the preferred orientation in terms of grain numbers, not grain areas; larger grains were weighted equally with small ones. No preferred orientation is expected on this basis at the chill surface. In a later paper,' Edmunds stated that experiments show a random grain orientation at the surface in die cast aluminum; his technique, also used in his earlier paper, takes account of grain area. Little work has been published on the dendritic structure of metal chill grains. Recent work of Biloni and Chalmers on "predendritic growth" shows the change in morphology from spherical to dendritic during the initial stages of freezing, 5 but this work did not include detailed examination of the fully developed dendrites. Other pertinent work includes that of Lin-denmeyer, who investigated the growth of ice dendrites. 6 When growth was on a substrate, the dendrite axes were bent. The bend corresponded to a change in orientation of the crystal lattice and occurred in such a way as to align the basal plane to the substrate. DENDRITE STRUCTURE Fig. 1 shows the chill surface of a typical casting poured above the critical temperature necessary to produce coarse grains. A cursory examination of these grains shows that the surface dendrite arms within most of the grains are oriented roughly perpendicular to each other. One is tempted to assume that these are (100) directions and that, therefore, marked preferred orientation exists at the chill face. This, however, is not the case. Each of the grains in the casting of Fig. 1 was separately identified, Fig. 2, and its orientation determined by the Laue back-reflect ion method. Results are given in Fig. 3 and it is seen there that no preferred orientation exists. Even when grain area is accounted for, there is no significant preferred orientation. The relationship between surface grain structure and crystal orientation was then obtained by assigning X and Y axes to the casting surface, Fig. 1, and assigning the same axes to the stereographic projections of each grain. Thus, the visible surface structure could be compared readily with grain orientation. This was done for fifty-five of the grains of Fig. 1. Results of this study on three typical grains are described below, and some general observations given subsequently. Fig. 4 shows the structure and stereographic projection of a grain which lies near the (100) zone (with respect to the casting surface). The X and Y directions are marked on the projection, and the photomicrograph mounted with the same orientation. Poles of the stereographic projection represent crys-tallographic directions in the grain which point out of the casting, toward the chill. Two (100) directions are shown in Fig. 4. A line joining the center of the projection and a pole represents the projection of the pole onto the X-Y plane (chill surface). Two such lines are shown in Fig. 4 (solid lines). A line joining the intersection of a great circle with the circumference of the projection gives the trace of a crystallo-graphic plane in the chill surface; two such traces are shown (dashed lines).

Jan 1, 1968

By C. E. Lundin

The Ce-H system was investigated in the temperature range, 573° to 1023°K, and the pressure range, 10-3 to 630 Torr, as a function of 'composition up to 72 at. pct H. Families of isothermal arid isopleth curves were plotted from the pressure-terr~perature-composition relationships. From these curves the solubility relationships were determined for the system. The isopleths are analytically represented by equilibrium dissociation pressure equations. The relative partial molal enthalpzes and entropies of solution of hydvogen in the systerrz were calculated fronz the dissociation pressure equulions and are tabulated. The integral free energies, enthalpies, and entropies of mixing in the Ce-H system were determined from the relative partial quantities and are also tabulated. The standard free energy, enthelpy, and entvopy of reaction of the dihydride phase at kcal per kcal per mole H2, and ?S° = -34. 1 cal per deg mole H2, respectively. The equilibrium dissociation pressure equation in the two-phase region is: UNTIL recently very little was known of the detailed solubility and thermodynamic relationships of the Ce-H system. Two previous investigations1,2 are noteworthy. However, significant discrepancies and omissions exist on analyzing them. The work of Mulford and Holley1 on cerium did not clearly delineate the boundaries of the two-phase region, Cess - CeH2-x. The plateau partial pressures were not thoroughly defined and were considerably displaced in pressure compared to those from the work of Warf and Korst.2 These latter authors concentrated their studies primarily from 823° to 1023°K in the pressure range of 1 to 760 Torr. No data were determined to outline the regions of primary solid solubility and the hydride phase. Also the establishment of the plateau partial pressures was rather limited in scope. In neither work was a treatment conducted of the relative partial molal enthalpies and entropies of solution of hydrogen in the single-phase regions and the integral thermodynamic quantities of mixing throughout the system. Therefore, it was the objective of this research to determine the complete equilibrium solubility relationships and thermodynamic data for the system by pressure-temperature-composition studies. EXPERIMENTAL PROCEDURE The cerium metal for this study was donated by the Reno Metallurgy Research Center of the Bureau of Mines. Total impurity content was 0.13 pct with only 60 ppm O. The metal was checked metallographically and contained only minor amounts of second phase compared to cerium from other sources. Specimen preparation was done in a dry box flushed with argon gas. The surface of a small rectangular piece of cerium (about 0.2 g) was filed with a clean, mill file. Final weighing was done in a tared enclosed vial containing argon gas. The specimen was then loaded quickly into the reaction chamber which was purged several times with high-purity hydrogen gas and then allowed to pump to about 10-6 Torr. The furnace was heated to the reaction temperature and the run started. The equipment used to conduct the hydriding was a Sievert's-type apparatus. Basically it consisted of a source for pure hydrogen, a precision gas-measuring burette, a heated reaction chamber, a McLeod gage, and a mercury manometer. Pure hydrogen was supplied by the thermal decomposition of uranium hydride. The 100-ml precision gas burette was graduated to 0.1-ml divisions and was used to measure the quantity of gas and admit it to the chamber. The reaction chamber was a quartz tube. Prior to each run, the cerium specimen was wrapped in a tungsten foil capsule to prevent reaction of the cerium with the quartz. Control of the temperature was achieved within ±1°K. Pressures in the manometer range were measured to ±0.5 Torr and in the McLeod range (10-3 to 5 Torr) to ±3 pct. The compositions of hydrogen in cerium were calculated in terms of hydrogen to cerium atomic ratio. These compositions were estimated to be ±0.01 H/Ce ratio. The technique used to study the equilibrium pressure-temperature-composition relationships of the Ce-H system was to develop experimentally a family of isothermal curves of composition vs pressure. The range of pressure through which each isotherm was developed was from 10-9 to about 630 Torr in the temperature interval, 573° to 1023°K. RESULTS AND DISCUSSION The hydriding characteristics of cerium are iso-morphous with those of the elements of the light-rare-earth group (lanthanum, cerium, praseodymium, and neodymium) wherein the region from the dihydride to trihydride is continuously single phase.' The structure of this phase is fcc.3 The heavy rare earths form a trihydride,2 which is hcp, separated by a two-phase region from the fcc dihydride phase. The Ce-H system is represented by the family of experimental isotherms in Fig. 1. Due to the small scale required to draw the curves, the experimental points are omitted; however, a total of 240 experimental data points were taken to prepare these curves. The solubility relationships can be deduced therefrom. Three distinct regions of partial pressure and composition can be seen. The region of cerium solid solution is represented by the rapidly rising isotherms in the dilute composition range. In accordance with Gibbs Phase Rule only one solid phase, the cerium solid so-

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

By Kun Li, Alex Simkovich

The rate of dissolution of alumina in carbon-saturated liquid iron has been studied experimentally in a system where alumina was in the form of a cylindrical rod immersed in an iron bath contained in a graphite crucible. Data obtained consisted of the concentrations of aluminum in the melt as a function of time. In the case of static experiments, the data are shown to agree with theoretical prdictions based on the diffusion of aluminum.. The rate of dissolution was greatly increased by the rotation of the alumina rod. It is concluded that the diffusion of aluminum from the alumina/metal interface is the rate-controlling step. In the past, thermodynamic investigations of systems encountered in ferrous process metallurgy have received widespread attention. More recently, considerable work has been devoted to the study of kinetics associated with these systems in an effort to determine their rate controlling mechanisms. The alumina-iron system is of great importance in ferrous metallurgy. Yet information concerning kinetics of reaction in this system is seriously limited. The present study was made in order to establish the rate-controlling step for dissolution of solid alumina in liquid iron. LITERATURE REVIEW A number of papers concerning dissolution of solid metals in liquid metals have been reported in the literat~re. Generally, for these simple systems, dissolution is controlled by mass transfer of the dissolving species. Complex systems involving dissolution of solid metal carbides and oxides in liquid metals and slags have been studied to a much lesser extent. Skolnick5,6 reported on the reaction between liquid cobalt and poly-crystalline cylinders of tungsten carbide, in which the cylinders were dissolved while being rotated about their longitudinal axes at various speeds and temperatures. As a result of unexpected preferential grain boundary attack by the liquid cobalt, large errors in the measured dissolution rates occurred because of loss of tungsten carbide grains to the liquid cobalt. Nevertheless, it was possible to establish that the liquid Co-W carbide reaction was not controlled by mass transfer. In a similar approach, cooper7 was able to show that artificial sapphire rods, (alumina single crystals) dissolving in lime-alumina-silica slags obeyed a mechanism of mass transfer control. Here, again, the rods were rotated at various speeds and temperatures, and the process was followed as a function of these variables. Forster and Knacke8 took a practical approach to reaction between slags and refractories. By blowing argon through refractory cylinders of silica, silli-manite, or dolomite and directing the gas to rise along the slag-refractory interface, it was possible to increase the rate of mass transfer. Although the method was admittedly crude, it nevertheless permitted an evaluation of the relative stabilities of refractories with respect to slag attack. Data were interpreted on the basis of mass transfer control. EXPERIMENTAL TECHNIQUE Apparatus. An illustration of the apparatus used in this study is shown in Fig. 1. The furnace consisted of a Morganite recrystallized alumina tube wound with a molybdenum coil. A secondary molybdenum heater was mounted around the upper half of the primary coil to aid in controlling the thermal gradient within the furnace. The primary heater tube was 3 in. in ID and 30 in. long. A reducing mixture of 95 pct N and 5 pct H was maintained around the heating elements. Thermal insulation was provided by alumina powder. The chamber within the primary combustion tube contained a boron nitride block near the top to assist in controlling the thermal gradient to the furnace and also to provide a bearing surface for the rotating graphite shaft. The outside diameter of the graphite shaft was $ in. A separate threaded graphite specimen holder was screwed into the end of the shaft. The holder contained a tapered hole drilled into the end to guide the oxide specimens as they were pressed into it for mounting. Additional guidance for the rotating graphite shaft was furnished by a water-cooled bronze bushing attached to the top of the furnace. A steel clamp was fastened to the upper end of the graphite shaft and rested on a thrust bearing; the shaft and clamp were driven by a dc motor through a set of gears. Two O-rings located immediately above the bronze bushing maintained a gas-tight seal about the graphite shaft. The lower half of the alumina tube housed the crucible and charge, which were placed on a 3/4-in. diam movable alumina support tube. With this arrangement, charges could be inserted into or removed from the furnace while the hot zone was maintained at or above 1000°C. To control the temperature of the furnace, the thermocouple was mounted inside the support tube and in contact with the crucible bottom. Stray electric fields in the furnace were of sufficient intensity to cause erratic indications by the thermocouple. By enclosing the thermocouple protection tube in a molybdenum sheath and grounding this shield, the problem was eliminated. Output of the thermocouple went to an automatic continuous balance controller. Procedure. A typical run was as follows. First, electrolytic iron was premelted in graphite crucibles and cast into graphite molds with the same configura-

Jan 1, 1970

By Winston A. Wong, John J. Jonas

Commercial purity aluminum was deformed by extrusion over the temperature range 320° to 616°C and the strain rate range 0.1 to 10 per sec. Flow stresses and strain rates were calculated from the experimenLa1 ram pressures and speeds. The stress-strain rate-lemperature relationship in extrusion was found to be similar to that in creep. Extrusion, torsion, compression, and creep data extending over ten orders of magnitude of strain rate and over two orders of magnitude of stress were correlated by a single creep equation. It was concluded that hot-working is a thermally activated process, in which the rate-controlling mechanism is either the climb of edge dislocations or [he motion of jogged screw dislocations. The microstructural changes observed during extrusion were consistent with the proposed deformation mechanisms. ALTHOUGH great progress has been made in understanding the technology of extrusion, very little is known about the actual deformation mechanisms operating during flow. Previous accounts describing extrusion have indicated that the relationship between ram speed (V), pressure (P), and temperature (T) can be given as follows:1 V = apb and P = A&apos; exp(-AT). In these equations, a and b are constants which depend on temperature, A&apos; is a constant which depends on ram speed, and A is a "coefficient" with a different value for each metal. Although these equations have fairly wide application, they do not contribute much to a fundamental understanding of the deformation. Furthermore, extrusion has not hitherto been considered as a thermally activated rate process. This lacuna is surprising because hot-working is similar to high-temperature creep in several respects. There is, in fact, a fair body of experimental evidence suggesting that the material response under hot-working conditions is similar to that occurring under creep conditions, in spite of the many orders of magnitude difference in strain rate.2"4 Since creep has been extensively analyzed in terms of dislocation mechanisms, the comparison of hot-working to creep is useful, for it can suggest the possible deformation mechanisms operating during hot-working. In this paper, the hot extrusion of aluminum will be examined from the point of view of thermally activated deformation mechanisms, such as operate during creep. EXPERIMENTAL PROCEDURE The experimental procedure consisted of extruding commercial purity aluminum* over a range of ram velocities and temperatures at constant die reduction by the direct method. Details of the experimental equipment have been published elsewhere.5 Extrusion was carried out at each of the following billet temperatures: 320°, 376°, 445°, 490°, 555°, and 616°C at the following constant ram speeds: 0.002, 0.008, 0.02, 0.1, and 0.2 in. per sec.* All results were obtained using a square-shouldered die with an extrusion ratio of 40:1, giving a reduction in area of 97.5 pct. The ram force was the dependent variable, and was measured by means of strain gages on the ram and was plotted as a function of ram travel. The sequence of events before making an extrusion was duplicated before each run so as to minimize as much as possible variations in experimental conditions. For example, after the equipment had been assembled, the billet was allowed to heat up to temperature inside the insulated container. Once the container attained the desired temperature, a period of 1/2 hr was allowed to elapse before the extrusion was made. This time was found to be required to allow the billet to reach a steady-state temperature, as determined from previous tests. When all was ready, extrusion was carried out without interruption; that is, the billet was upset and extruded in one operation. EXPERIMENTAL RESULTS AND DISCUSSION The two usual experimental approaches for investigating high-temperature deformation exhibit an important common feature. In the first approach, which corresponds to creep, a constant stress (or load) is applied to the material at constant temperature and the resultant strain is recorded against time. After an initial transient stage, a state of constant strain rate exists (secondary creep), in which a steady-state condition is established which is sensitive to variation in either applied stress or temperature. In the second approach, a constant strain rate is applied and the resultant flow stress is recorded. This corresponds to the situation in hot torsion or hot compression, where it is observed that, for a constant test temperature, there is an initial rise in stress to a steady value which is maintained up to very high strains. In tests of this type, a steady-state region is also established in which the stress is sensitive to variation in either the strain rate or the temperature.3,4,6-16 In both types of tests, therefore, a steady-state region is established after an initial transient. In the case of hot-working this region may be called steady-state hot-working, and it is analogous to steady-state creep with which it has many common features. Stress Dependence of the strain Rate in Extrusion. In order to assess the stress dependence of the strain rate under extrusion conditions, and to compare it to that of creep, as well as of hot torsion and hot compression, the extrusion data were analyzed according to power, exponential and hyperbolic sine creep equations.

Jan 1, 1969

By James M. Barker, George S. Austin

Stone, one of the oldest building materials, today remains a well-established material throughout the construction industry. The use of natural stone is much less prevalent now than in the past. It is still widely considered to be the most aesthetically pleasing, prestigious, and durable building material. New and re-opened quarries are coming onstream to meet increased demand related to new building technology and increased residential use of stone. CLASSIFICATION No classification can completely eliminate overlap between dimension stone, aggregate, and decorative stone because most stone is multi-purpose. Many used for decorative purposes are not produced specifically for that end use. Rock otherwise considered waste in dimension stone or aggregate quarries can be decorative stone coproducts (Fig. 1). Many uses require a compromise between decorative and structural qualities (Bowles, 1992, written commu¬nication). Shipley (1945) used decorative stone interchangeably with or¬namental stone. Gary et al. (1972) defined decorative stone as that used for architectural decoration, such as mantels, columns, and store fronts, but added that it is sometimes set with silver or gold in jewelry as curio stones. Bates and Jackson (1987) also restricted decorative stone to that used for architectural decoration. Meanings of otherwise identical terms used in the stone industry differ be¬tween geologists, engineers, and quarriers. They often carry a much broader meaning for quarriers and engineers compared to their very specific use by geologists (Makens et al., 1972). Decorative stone, including ornamental stone, is more broadly defined by geologists as any stone used primarily for its color, texture, and general appearance. It is not used primarily for its strength or durability, such as construction stone, or in specific sizes, such as dimension stone. The decorative stone industry uses a much wider range of stone types compared to stone that is dimensioned. Decorative stone usually serves some structural pur¬pose, but is not load-bearing to any great extent. Weak or costly stones serve in decorative, not structural, applications. STATISTICS AND END USES Decorative and dimension stone data are difficult to separate because the US Bureau of Mines keeps statistics only on dimension stone and crushed stone. The value of domestic dimension stone production in 1990, which includes some decorative stone, was about $210 million compared to imports of about $524 million and exports of about $35 million. Production was 1 080 t of which at least one-third was for decorative uses (Taylor, 1992). The principal uses are rough blocks in building construction (23%) and monu¬ments (18%); the remainder is used as ashlar (18%), curbing (12%), and miscellaneous (29%). Major rock types are granite (50%), limestone (30%), sandstone (10%), slate (3%), marble (2%), and other (5%) (Harben, 1990). Crushed stone valued at $5.6 billion was produced in the United States in 1990 by 1700 companies operating 3400 active quarries in 48 states (Tepordei, 1991). About 52% is used in con¬struction, 9% in cement and lime manufacturing, 2% in agricul¬ture, 2% in industrial uses, and 35% for unspecified uses including decorative aggregate. Limestone and dolomite comprise about 71%, granite 14%, and traprock 8% of the stone crushed in the United States. The remaining 7% are, in descending quantity, sandstone, quartzite, miscellaneous rock, marble, shell, calcareous marl, volcanic cinder and scoria, and slate. The basic types of decorative stone are: rough stone, aggregate, cut or dressed stone, and manmade stone [(Table 1)]. Rough Stone Rough stone is used as it is found in nature with very limited processing such as minor hand shaping, edge fitting, and size or quality sorting (Perath, 1992, written communication). This stone type is often marketed locally in relatively small tonnages and includes fieldstone and flagstone. The primary end uses of rough stone are landscaping, edging, paving, or large individual stone landscape or interior accents [(Fig. 2)]. Fieldstone: Fieldstone is picked up or pried out of the ground (gleaned) without extensive quarrying and includes garden or large landscaping boulders (Austin et al., 1990, Hansen, 1969). Boulders and cobbles may be split or roughly trimmed for use in rubble walls and veneers, both interior and exterior. Popular fieldstone rock types include sandstone, basalt, limestone, gneiss, schist, quartzite, and granite, but many others are suitable. Much fieldstone is col¬lected by individuals or small companies because the industry is labor intensive and markets are small. The stone may be sold locally in small quantities from the back of vehicles (Austin et al., 1990). Fieldstone includes many rock types, sizes, and shapes with the only common denominator that it must be set by hand and be durable (Power, 1992, written communication). Moss Rock. Moss rock is fieldstone partially covered by algae, mosses, lichens, and fungi that give the rock an aged and variegated patina (Austin et al., 1990). The plants are supported by moisture and nutrients in the stone. Moss rock is used for landscaping, walls, and fireplaces. Although almost any durable rock can be a moss rock, most are slabby or rounded sandstone and limestone (Fig. 3). Flagstone: Flagstone or flagging consist of thin irregular slabs used for paving, walkways, and wall veneers. Random-shaped flagging is produced widely in the United States. Suitable stone

Jan 1, 1994

By P. L. Weston, S. E. Khalafalla

A systematic study was made by the Bureau of Mines on the effect of so me hypothesized accelerators for the process of wustite reduction in carbon monoxide. When small concentrations of promoter materials in the order of 0.69 at. pct were added to the reducible charge, the rate of reduction to iron was increased. Promotion phenomenon prediction was made in light of a suyface reduction mechanism with the aid of Vol&apos;kenshtein&apos;s effect regarding the propagation of crystal lattice disturbances by small amounts of relatively larger interstitial ions. The acceleration produced by a typical promotor, such as potassiunl, increases with protnoter concentration up to a maximum, beyond which the reduction rate decreases. Concentration for maximum promotion depends on the nature and physicochemical properties of the promoter. The extent of reduction rate enhancement is found to be directly proportional to the atomic volume and electronic charge of the additive. DESPITE the enormous volume of literature on iron oxide reduction, very little is reported concerning additive or impurity effects on this important metallurgical process. The beneficial effect bf calcium compound additions on the reducibility of iron oxide sinters has been reported by Tigerschiold,1 vor dem Esche,2 and Edstrom. Doi and Kasai~ found that the addition of lime or limestone to iron ores helps to break up any unreducible compounds, such as fayalite or ilmen-ite. and thus free the combined iron for reduction. Schenck et al. 5 suggested that the increased reduction rate obtained when adding lime could be accounted for by the instability of wustite in the presence of lime. Acid-base slagging reactions resulted in wustite disproportionation according to The dicalcium ferrite formed will yield iron and calcium oxide during reduction. Regenerated calcium oxide dissociates more wustite. This mechanism has been used by Seths and white7 to explain their experimental results. Recently, Strangway and ROSS&apos; attributed the calcium carbonate acceleration of iron oxide agglomerate reduction to increased porosity, both initial as well as that developed during reduction. Aside from calcium carbonate, or oxide, no other promoter was noted in the literature, except for a brief mention by Barrett and woodg on the effect of sodium carbonate and aluminate as activators for the hydrogen reduction of magnetite at 600°C. The present investigation systematically studied a host of other promoters, including calcium and sodium, in an attempt to elucidate the mechanism by which promotion takes place and to fit the results into a simple chemical model. To attain this goal, the effect of promoter physical properties, such as atomic volume, electronic charge, and concentration are related to wustite reduction kinetics in this paper. Wustite reduction to iron, rather than the overall hematite reduction, was chosen since this reaction is known to be the slowest, and hence the rate-deter mining step for the overall iron oxide reduction process. EXPERIMENTAL PROCEDURE Raw Materials and Their Preparation. The pure or impregnated wustite pellets were prepared from minus 400-mesh chemically pure hematite powders. A known weight of hematite was thoroughly and uniformly mixed with a calculated weight of the additive. The mixed paste containing 35 wt pct water was gradually heated from 400" to 1200° C and fired at 1200°C for approximately 4 hr in an air atmosphere. After cooling, the sinter was pulverized to minus 100 mesh and pelletized into minus 4- plus 5-mesh spheres. Pellets were fired, similarly to the paste mix, air-cooled, sized, and stored. An appropriate weight of the charge (20 g) was placed in a zirconia reduction tube maintaining a uniform oxide bed height of 1 cm and a cross section of 7.1 sq cm for all of the test runs. The samples were supported in the vertical reaction tube by a bed of fragmented insulating firebrick plus 3- to 6-mesh alumina beads. The hematite was then transformed to wustite by reduction with a 30 pct CO2-70 pct CO gas mixture at 1000°C in a globar furnace. Complete conversion to wustite was ascertained by a continuous infrared gas analyzer recording the CO-CO2 content of the effluent gas until no carbon monoxide was absorbed from the inlet gas, and inlet-outlet gas analysis remained constant for 30 min. The wustite sample was then reduced with 100 pct CO at 100WC. From the recorded data, an initial rate of reduction was determined by the initial slope of the graph percent reduction vs time. In order to estimate the accuracy of the data, five separate determinations of the reduction curve of pure wustite, under otherwise identical conditions, were performed. The maximum deviation from the average reduction at 14 min amounted to 2 2 pct reduction. This deviation corresponds to 3.8 pct variation based on the percent reduction of the sample. Aiiy impurity effect below the limits of this maximum deviation was considered a spurious result. If the effect exceeded + 4 pct, then it was considered as a positive one. Considerable care was exercised in determining the initial rate from the slope of the initial segments of the curve. Each reduction curve was examined separately on large graph paper and the best tangent to the curve at zero time was drawn. The slope of this tangent was taken as a measure of the initial fractional reduction per minute. Although the time required to reach 50 pct reduction may be of special practical significance, initial rate measurements are invaluable in fundamental studies. These rates provide a measure of the process kinetics on the initial

Jan 1, 1968

By John W. Burd

A system is described for the simultaneous deposition of epitaxial layers on as many as eight substrates. A high degree of uniformity of both physical and electrical characteristics is achieved in the films. Variation of film thicknesses is consistently less than ±10pct within a wafer and from wafer to wafer within a run with the variation typically on the order of 55 pct. Composition variation of GaAs1-x PX layers within a wafer and from wafer to wafer within a run is consistently less than 51 pct. Electrical evaluation of the films by several techniques indicates excellent doping uniformity within a wafer and from wafer to wafer within a run. Mobilities for lightly doped GaAs films at 300°K are consistently >6000 cm2 v-1 sec-1 and mobilities > 7000 cm2 v- 1 sec-1 are regularly attainable. Techniques for the preparation of material with carrier concentrations from 1 x 1015cm-3 to 1 x 1019 cm-3 n-type and 5 x 1016 to 5 x 1018 cm-3 p-type are discussed. METHODS for the preparation of 111-V compounds by vapor phase reactions have been extensively reported in the literature.1-6 Almost all of the apparatus described for these various methods are suitable for processing one or at the most a very limited number of wafers simultaneously. With the recent rapid advances in the use of vapor grown GaAs for microwave oscillators and GaAs1-xPx as visible light emitters the requirements for these materials are steadily increasing. In order to satisfy these requirements it is necessary to move from a laboratory scale apparatus to one which is capable of processing a large number of wafers simultaneously. Desirable features would be a high degree of uniformity among the wafers and good reproducibility from run to run. The apparatus to be described fulfills these requirements very well. DISCUSSION The various methods reported in the literature can be classified under three headings: 1) closed tube, 2) open tube, and 3) the close-spaced method. Of these three the open-tube method is the most amenable for scale-up to a manufacturing process. It is the most versatile and the various operating conditions can be more precisely controlled than with the other two methods. A number of chemical reactions may be used to achieve vapor-phase growth of 111-V compounds. Sev-era1 of the more generally used reactions are shown in Fig. 1. All of these reactions have the following points in common: 1) generation of a volatile group III(Ga) species by the reaction of the transport agent (halide or HC1) with either Ga or GaAs, 2) introduction of the Group V(As and/or PI component, 3) a method of adding dopant, if desired, and 4) a region in which deposition from the vapor will occur and form as a single crystal epitaxial film on the substrates. The laboratory scale reactors permit the hot re-actant gases to flow into the relatively cooler deposition zone and pass successively over the several substrates which are arrayed along the long axis of the tube parallel to the gas flow. With this arrangement the composition of the reactant stream is continually changing as solid material is deposited on each successive substrate. As a result of this changing gas composition the reaction driving force also changes from substrate to substrate and the degree of uniformity of layer thickness, doping level, and so forth, is poor. This effect can be partially overcome by imposing a controlled temperature gradient along the deposition region to compensate for change in gas composition. However, even when this is done variations in layer thickness on the order of 30 to 40 pct are common and as high as 50 pct are frequently experienced between adjacent wafers in the tube. To expand this arrangement to a large number of wafers would only increase the nonuniformity from the first to last wafer in the line. From the above discussion the two undesirable features of changing gas composition and temperature gradient become evident. A reactor system which eliminates or minimizes these undesirable features is one in which the apparatus is mounted vertically as shown schematically in Fig. 2. The vertical mounting permits the disposition of a number of substrates on a suitable support so that all wafers are at the same vertical height in the furnace and hence at essentially the same temperature. By using only a single row of wafers the reactant gas mixture passes over only one substrate in its path through the reactor. Thus the two undesirable features of changing gas composition and temperature gradient are minimized. An additional design feature which further minimizes temperature variations is rotation of the substrate holder. Rotation serves to integrate any radial temperature gradient existing around the resistance heated furnace. A photograph of a reactor assembly at the completion of a run is shown in Fig. 3. MATERIAL PREPARATION Apparatus. Although any of the several chemical systems shown in Fig. 1 are adaptable for use in this apparatus the one generally used is System 2, the hydride synthesis system. This system has been de-

Jan 1, 1970

By K. R. Carson, J. Weertman

An attempt is made to ascertain the mechanism of tangle and cell formation and its dependence upon dislocation-interstitial carbon interactions. The strain-hardening behavior of single crystals of 3.25 pct Si-Fe was determined at 300° and 425°K and under conditions of both continuous and interrupted tensile strain. Significantly enhanced hardening was observed in crystals deformed at the elevated temperature, and it was further accentuated by interrupted straining. Transmission electron microscopy was used to study the resultant dislocation structures. Strain aging was found to aid tangle and cell formation at 425°K, but at both temperatures embryo tangles formed solely from primary glide dislocations, presumably by a process involving cross slip and "mushrooming". IN the course of plastic deformation all bcc metals and alloys develop a dislocation structure characterized by loose-knit groups of tangled dislocations. With increasing strain the tangles become more tightly knit and grow larger; finally a three-dimensional cellular substructure is formed:1 This process has been observed with the transmission electron microscope.&apos;-l7 However, most investigations were confined to the study of nearly pure polycrystalline metals at relatively low temperatures. At intermediate temperatures, 0.17 to 0.14 Tm where T, is the melting temperature in degrees absolute, the mobility of interstitial impurities such as carbon is high enough to permit migration to nearby glide dislocations but is still low enough so that a significant drag force is exerted.18,19 it is also in this temperature range that a hump occurs in the curve of work-hardening rate vs temperature for iron. Analogous plots for tantalum" and columbiumzo show a definite upward trend in the work-hardening rate. Keh and Weissman1 have pointed out that this behavior may be explained solely on the basis of changes in the dislocation configuration: at low temperatures the dislocations tend to be relatively straight and uniformly distributed, but at intermediate temperatures tightly knit tangles and cellular substructure appear. The interference of these tangles with glide dislocations causes the observed increase in the work-hardening rate. This explanation appears reasonable, yet one might ask what factors cause tangle formation to be so favorable at intermediate temperatures. It seens likely that the strong dislocation-interstitial interactions which are known to occur in this temperature range are at least partly responsible," with the magnitude of the effect being proportional to the interstitial concentration. The purpose of the present work is to study the relationship between tangle formation and strain hardening in a bcc metal in the temperature range 0.17 to 0.4 Tm. Particular emphasis was placed upon a study of the effects of interstitial-dislocation interactions. Single crystals of 3.25 pct Si-Fe containing about 200 ppm of C in solid solution were used in the investigation for the following reasons: 1) The mobility of interstitial carbon in 3.25 pct Si-Fe is negligible at 300°K but increases rapidly at slightly elevated temperature22. Hence, differences between the flow curves and dislocation structures of crystals deformed at 300°K, 0.17 T,, and crystals deformed, say, at 425°K, 0.24 Tm, should be appreciable because of the enhanced dislocation-carbon interactions at the elevated temperature. This effect was accentuated in some samples by interrupted straining, thereby introducing a certain amount of aging. 2) Near room temperature, slip in suitably oriented 3.25 pct Si-Fe single crystals is largely confined to the (110) planes.23&apos;24 Dislocation structures formed under conditions of single glide are the least complicated and their method of formation is the most easily discernable. 3) Dislocations in Si-Fe can be tightly locked with carbon atmospheres by a low-temperature aging treatment. The subsequent thinning of samples to foil thicbess causes little or no rearrangement in the dislocation structure.25 EXPERIMENTAL PROCEDURE Large single-crystal sheets of 3.25 pct Si-Fe were donated by Dr. C. G. Dunn of the General Electric Research Laboratory, Schenectady, N. Y. The orientations of the sheets were determined and slabs 1.0 by 0.25 by 0.05 in. were cut such that the desired tensile axis corresponded to the long dimension. The slabs were mechanically polished and subsequently decar-burized by heating at 1000°C for 3 days in a flowing wet-hydrogen atmosphere. A carbon content of about 200 ppm was introduced by heating at 805°C for 25 min in a flowing atmosphere of dry hydrogen containing heptane vapor. Shaped copper tools were then used to spark-machine at 0.125 by 0.50 in. gage length onto each slab. Vacuum annealing at 1225°C for 2 days followed by a quench into the cold end of the furnace to retain carbon in solid solution concluded the soecimen preparation. Continuous tensile flow curves for crystals of severa1 orientations Were obtained both at 300&apos; and 425°K. A strain rate of 6.67 x 10-4 Per set was used in these and all other tests. Crystals oriented for single glide, B and D in Fig. 1, were subjected to a 3.5 pct plastic elongation to insure uniform slip along the gage length; they were then immediately subjected to interrupted strain cycling as indicated in Fig. 2(a). Each cycle consisted of unloading to 1.5 kg per sq mm, holding

Jan 1, 1969

By W. N. Poundstone, P. C. Thakur

Introduction Horizontal drilling in coal mines is a relatively new technology. The earliest recorded drilling in the United States was done in 1958 at the Humphrey mine of Consolidation Coal Co. for degasification of coal seams. Spindler and Poundstone experimented with vertical and horizontal holes for several years. They concluded in 1960 that horizontal drilling in advance of underground mining appeared to offer the most promising prospect (for degasification) but effective and extensive application would be dependent upon the ability to drill long holes, possibly 300 to 600 m, with reasonably precise directional control and within practical cost limits (Spindler and Poundstone, 1960). Mining Research Division of Conoco Inc., the parent company of Consolidation Coal Co., began a research program in the early 1970s to achieve the above objective. The technology needed to drill nearly 300 m in advance of working faces was developed by 1975 and experiments on advance degasification with such deep holes began in 1976. Preliminary results of this research have already been published (Thakur and Davis, 1977). To date nearly 4.5 km of horizontal holes have been drilled for advance degasification and earlier results were reconfirmed. In summary, these are: • The greatest impact of these boreholes was felt in the face area where methane concentrations were reduced to nearly 0.3% in course of two to three months from original values of nearly 0.95%. • The methane concentration in the section return reduced to 50% of its original value immediately after the boreholes were completed, indicating a capture ratio of 50%. • The total methane emission in the section (rib and face emission plus the borehole production) did not increase but rather gradually declined with time. • Initial production from 300 m deep boreholes in the Pittsburgh seam varied from 3 m3/min to 6 m3/min but then slowly declined as workings advanced inby of the drill site (well head) exposing a larger surface area parallel to the borehole. Encouraged by these results, it was decided to design a horizontal drilling system that would be mobile and compatible with other face equipment. A mobile horizontal drill can be divided into three subsystems: the drill rig, the drill bit guidance system, and borehole surveying instruments. The drill rig provides the thrust and torque necessary to drill 75- to 100-mm diam holes up to 600 m deep and contains the mud circulation and gas cuttings separation systems. The drill bit guidance system guides the bit up, down, left, or right as desired. Borehole surveying instruments measure the pitch, roll, and azimuth of the borehole assembly. Additionally, it also indicates the thickness of coal between the borehole and the roof or floor of the coal seam. Thus, it becomes a powerful tool for locating the presence of faults, clay veins, sand channels, and the thickness of coal seam in advance of mining. In recent years, many other potential uses of horizontal boreholes have come to light, such as in situ gasification, longwall blasting, improved auger mining, and oil and gas production from shallow deposits. The purpose of this paper is to describe the hardware and procedure for drilling deep horizontal holes. The Drilling Rig [Figures 1 and 2] show the two components of the mobile drilling rig: the drill unit and the auxiliary unit. The equipment (except for the chassis) was designed by Conoco Inc. and fabricated by J. H. Fletcher and Co. of Huntington, WV. The drill unit. It is mounted on a four-wheel drive chassis driven by two Staffa hydraulic motors with chains. The tires are 369 X 457 mm in size and provide a ground clearance of 305 mm. The prime mover is a 30-kw explosion-proof electric motor which is used only for tramming. Once the unit is Crammed to the drill site, electric power is disconnected and hydraulic power from the auxiliary unit is turned on. Four floor jacks are used to level the machine and raise the drill head to the desired level. Two 5-t telescopic hydraulic props, one on each side, anchor the drill unit to the roof. The drill unit houses the feed carriage, the drilling console, 300 m of 3-m-long NQ, drill rods, and the electric cable reel for instruments. The feed carriage is mounted more or less centrally, has a feed of 3.3 m, and can swing laterally by ± 17°. It can also sump forward by 1.2 m. The drill head has a "through" chuck such that drill pipes can be fed from the side or back end. General specifications of the feed carriage are: [ ] The auxiliary unit. The chassis for the auxiliary unit is identical to the drill unit but the prime movers are two 30-kW explosion proof electric motors. It is equipped with a methane detector- activated switch so that power will be cut off at a preset methane concentration in the air. No anchoring props are needed for this unit. The auxiliary unit houses the hydraulic power pack, the water (mud) circulating pump, control boxes for electric motors, a trailing cable spool, and a steel tank which serves for water storage and closed-loop separation of drill cuttings and gas.

Jan 1, 1981

By R. R. Jones, R. W. Kraft

Zn-Mg2Znn eutectic alloys nzay freeze willr either rodlike or lanzellar rnorphology. Alloys with slighlly more than /he eutectic arrzount of rnagnesillrn usually contain three-cnned dendrjles of MgzZnll in a eutec-lic ttlulris. All three morphologies haue the same cryslallographic orientution relationship: (0UOl) zn - 11 (111) Mg2Znll and (2310)Zn 11(101) Mg2Znll, but u3ith different prej-erred groulth direclions. The lurnellae lo rods transifion in con/rolled ingols qf euleclic cotnposition occurs because lhe large kinelic undercooling due to MgzZnll minirrzizes /he ejj-ecl of the solid-solid inlerface energy. The eutectic morphology is influenced by the presence of lhree-nned dendrites 0-f MgzZn11 which may conlrol /he rricroslrccture by acting as nuclealion sites. In recent years there has been much interest in eutectic solidification and several theories have been proposed. One of the confusing factors is the existence of various morphologies in which the solidified phases may form. The lamellar microstructure seems to be most common in metal eutectics, and it has been claimed&apos; that all regular eutectics should be lamellar if sufficiently pure. However, there still remain eutectic alloys which are not lamellar or which change their morphology as a function of growth conditions. The eutectic between zinc and the intermetallic phase Mg2Znll was chosen for this investigation because it has been found to solidify in more than one morphology. The diagram in anssen&apos; locates the eutectic point at 3.0 wt pct Mg and 367°C. lliott gives 364°C as the eutectic temperature, leaving the phase compositions unaltered. Since the growth conditions determine the micro-structure of the solidified alloy, the factors controlling the transition from one morphology to another could be studied. The lamellae to rods transition is of particular interest. PROCEDURE Alloys were prepared from carefully weighed portions of 99.999 pct Zn and 99.97 pct Mg by melting in Pyrex containers under argon and casting into graphite boats. The resulting ingots were remelted under argon and solidified unidirectionally in a horizontal tube furnace at growth rates ranging from 2.0 to more than 50 cm per hr under a temperature gradient, measured over a 5-cm length, of 9" to 14°C per cm. The solid-liquid interface appeared to be planar at all growth rates although no attempt was made to confirm this by decantation or quenching. A few ingots were allowed to freeze uncontrolled. Most alloys were of the nominal eutectic composition, 3.0 wt pct Mg according to Hansen2 and lliott, but some contained as much as 3.35 wt pct Mg. Chemical analyses were not run since metallographic examination confirmed that the desired composition was achieved. Specimens were cut from the middle portion of the ingot normal to the growth axis, polished mechanically, and etched with 2 pct Nital. Suitable areas were selected for the determination of crystallographic orientation relationships by a tiontechniqueof described previously by one of the authors.4 The (2310) planes of zinc and the (8701, {944}? (1032) planes of Mg2Znll were found suitable for orientation determination; experimental error was on the order of 2 or 3 deg. RESULTS Three different morphologies were found in the unidirectionally solidified alloys: lamellar eutectic, rod-like eutectic, and a structure whose most predominant characteristic was the presence of three-vaned (cellular) dendrites of Mg2Znll. These dendrites were only found in alloys with more than the eutectic amount of magnesium. In some ingots fine hexagonal needles of Mg2Znll surrounding a core of MgZn2 were observed. They were probably due to incomplete alloying and seemed to have no effect on the eutectic morphology. In addition hexagonal spirals like those discussed by Fullman and wood5 and Hunt and acksonh ere observed in some ingots frozen without directional control. Both MgZZn,, and MgZnz were detected by X-ray diffraction in these alloys. Since the morphology could not be grown unidirectionally and no characteristic orientation relationship between the phases was found, further study was limited to the lamellar: rodlike, and three-vaned dendrite morphologies. Alloys of Eutectic Composition, No Dendrites. The mcrostructures of allovs with no three-vaned dendrites were either lamellar or rodlike depending on the growth rate. At rates below 10 cm per hr the morphology was lamellar, consisting of two sets of parallel plates intersecting at about 54 deg like the Mg-MgzSn eutectic described by raft.7 At growth rates faster than 14 cm per hr the microstructure showed rods of zinc in a matrix of MgnZnll, while intermediate rates yielded mixtures of rods and lamellae in small groups. The lamellar "grains" were often several millimeters in cross section, but contained small irregular areas which divided each grain into perfect islands 100 or 200 p in diam. Lamellae were parallel to each other throughout the grain in spite of these defects in the structure, Fig. 1. Rods, on the other hand, could only be produced in small groups arranged like fish scales and separated by irregular areas of appreciable thickness, Fig. 2. Alloys Not of Eutectic Composition, With Dendrites. In alloys with 3.1 to 3.35 wt pct ME,-. three-vaned dendrites bf MgzZnll were usually found surrounded by eutectic. At growth rates slower than about 10 cm per hr the dendrites were separated from each other by small areas of both lamellar and rod eutectic, Fig. 3.

Jan 1, 1969

By I. Beukes, H. Kotze, B. Krause, R. P. Hattingh

Hillendale Mine is operated by Exxaro KZN Sands, and is situated on the north coast of KwaZulu-Natal in South Africa near the towns of Empangeni and Richards Bay, some 200 km north of Durban. During the mining operation the heavy minerals rutile, ilmenite, zircon and leucoxene are extracted for further beneficiation at a processing complex near the town of Empangeni. The deposit contains approximately 25% slimes (defined as the sub-45 micron fraction), and is mined using hydraulic monitoring. Run of mine is gravity fed down launders to pump stations, which deliver the material to a primary wet plant. Slimes is separated from the run of mine prior to the heavy minerals being separated from the sand. Sand tails containing approximately 2-5% slimes is pumped to the mining void. The slimes is thickened to a density of approximately 1.2, and most of the resultant material is pumped to a sub-aerial deposition site (residue dam). The area is characterized by an annual rainfall of approximately 1300 mm, which is relatively high by South African standards. From an agricultural perspective the soils are deep and well weathered. Dryland agriculture has been practised on an extensive scale in the area for the past 70 years. Sugar cane in particular is cultivated on and around the mine area. In terms of environmental approvals, the post-mining land use and objectives are defined as economically viable and sustainable sugar cane cultivation in the mined areas. During mining the soil profile is destroyed. In this paper the establishment of a reconstituted soil profile is discussed, with specific reference to the methodology that is being followed to achieve the homogeneous blending of sand and slimes. Defining the rehabilitation strategy and soil specification Strategically Exxaro KZN Sands divided rehabilitation into four aspects, comprising physical rehabilitation (restoration of soil structure), vegetative rehabilitation (restoration of vegetative cover), ecological rehabilitation (restoration of sustainable ecological communities), and sustainability (sustainable man/environment interface) (Hattingh and Viljoen, 2006). It is believed that the key to successful rehabilitation lies in achieving a substrate (soil) suitable for the establishment of the target vegetation. During the development of the rehabilitation strategy the key factor in the establishment of a suitable soil profile was shown to be the soil water retention of this material. Since dryland agriculture is practised, this aspect becomes critically important in ensuring that the post-mining land use is sustainable (Hattingh et al., in prep.). From a financial perspective, a closure certificate being issued implies that the state takes over financial liability for the rehabilitated land. This has significant implications for the state-the default position will be that all possible latent and residual impacts must be identified and known prior to a closure certificate being issued. From the mine&apos;s perspective this precautionary approach by the state implies that post-operational costs cannot be quantified exactly, and our approach is therefore to mitigate the risk of a long post-closure care and maintenance phase by means of addressing all potential latent defects during the operational rehabilitation phase. The financial viability of the soil reconstitution process itself is therefore not measured against other rehabilitation methods, but against the risk of not achieving closure. During a series of technical workshops comprising experts in the various disciplines in the rehabilitation of the soil profile were identified. These aspects include the re-establishment of a functional soil profile, soil physical characteristics, soil chemistry, soil biota, salinization potential, erodibility and soil weathering. The natural soils in the Hillendale area have been classified in terms of the South African soil classification system (MacVicar and co-workers, 1991) and consist of Hutton (orthic topsoils on red apedal subsoils) and Clovelly (orthic top soils on yellow apedal subsoils) soil forms. The topsoils consistently comprise medium to fine grained sand overlying heavier textured sandy clay loam to clayey subsoils. The topsoil structure consists of a single grain structure, whereas subsoils are apedal. These soils are typically deeply weathered and do not show secondary structures. During the mining process a layer of topsoil (300 mm) is stripped off, and the balance of the material down to the footwall is processed. Sand with 2-5% slimes (defined as the sub-45 micron fraction) is returned as backfill in order to re-establish the dune to approximate the previous landform. From an agricultural perspective this material is not suitable for the dryland cultivation of sugar cane. A capping of more suitable material therefore has to be provided. The most significant difference between the premining soil form and the backfill material is the percentage slimes, consequently a mixture of the sand and slimes is required as a capping over the backfilled sand. The required thickness of the cap is a function of specifically plant growth requirements, erodibility, weathering and runoff (Hattingh, et al.; in prep.). The percentage slimes required in the cap is a function of mainly soil water requirements (Hattingh and Viljoen, 2006). The conservative indications to date show that the reconstituted soil profile should consist of a homogeneously blended mixture of 70%-80% sand and 30%-20% slimes up to a maximum of 2 metres thick. This will be sufficient to ensure growth during dry periods.

Jan 1, 2007

By Fred C. Bond

MOST investigators are aware of the present unsatisfactory state of information concerning the fundamentals of crushing and grinding. Considerable scattered empirical data exist, which are useful for predicting machine performance and give, acceptable accuracy when the installations and materials compared are quite similar. However, there is no widely accepted unifying principle or theory that can explain satisfactorily the actual energy input necessary in commercial installations, or can greatly extend the range of empirical comparisons. Two mutually contradictory theories have long existed&apos; in the literature, the Rittinger and Kick. They were derived from different viewpoints and logically lead to different results. The Rittinger theory is the older and more widely accepted. In its first form, as stated by P. R. Rittinger, it postulates that the useful work done in crushing and grinding is directly proportional to the new surface area produced and hence inversely proportional to the product diameter. In its second form it has been amplified and enlarged to include .the concept of surface energy; in this form it was precisely stated by A. M. Gaudin2 as follows: "The efficiency of a comminution operation is the ratio of the surface energy produced to the kinetic energy expended. According to the theory in its second form, measurements of the surface areas of the feed and product and determinations of the surface energy per unit of new surface area produced give the useful work accomplished. Computations using the best values of surface energy obtainable indicate that perhaps, 99 pct of the work input in crushing and grinding is wasted. However, no method of comminution has yet been devised which results in a reasonably high mechanical efficiency under this definition. Laboratory tests have been reported&apos; that support the theory in its first form by indicating that the new surface produced in. different grinds is proportional to the work input. However, most of these tests employ an unnatural feed consisting either of screened particles of one sieve size or a scalped feed which has had the fines removed. In these cases the proportion of work" done on. the finer product particles is greatly increased and distorted beyond that to be expected with a normal feed containing the natural fines. Tests on pure crystallized quartz are likely to be misleading since it does not follow the regular breakage pattern of most materials but is relatively harder to grind at the finer sizes, as will be shown later. This theory appears to be indefensible mathematically, since work is the product of force multiplied by distance, and the distance factor (particle deformation before breakage) is ignored. The Kick theory&apos; is based primarily upon the stress-strain diagram of cubes under compression, or the deformation factor. It states that the work required is proportional to the reduction in volume of the particles concerned. Where F represents the diameter of the feed particles and P is the diameter of the product particles, the reduction ratio Rr is F/P, and according to Kick the work input required for reduction to different sizes is proportional to log Rr/log 2.5 The Kick theory is mathematically more tenable than the Rittinger when cubes under compression are considered, but it obviously fails to assign a sufficient proportion of the total work in. reduction to the production of fine particles. According to the Rittinger theory as demonstrated by the theoretical breakage of cubes the new surface produced, and consequently the useful work input, is proportional to Rr-1.5 If a given reduction takes place in two or more stages, the overall reduction ratio is the product of the Rr values for each stage, and the sum of the work accomplished in all stages is proportional to the sum of each Rr-1 value multiplied by the relative surface area before each reduction stage. It appears that neither the Rittinger theory, which is concerned only with surface, nor the Kick theory, which is concerned only with volume, can be completely correct. Crushing and grinding are concerned both with surface and volume; the absorption of evenly applied stresses is proportional to the volume concerned, but breakage starts with a crack tip, usually on the surface, and the concentration of stresses on the surface motivates the formation of the crack tips. The evaluation of grinding results in terms of surface tons per kw-hr, based upon screen analysis, involves an assumption of the surface area of the subsieve product, which may cause important errors. The&apos;evaluation in terms of kw-hr per net ton of 200 mesh produced often leads to erroneous results when grinds of appreciably different fineness are compared, since the amount of -200 mesh material produced varies with the size distribution characteristics of the feed. This paper is concerned primarily with the development, proof, and application of a new Third Theory, which should eliminate the objections to the two old theories and serve as a practical unifying principle for comminution in all size ranges. Both of the old theories have been remarkably barren of practical results when applied to actual crushing and grinding installations. The need for a new satisfactory theory is more acute than those not directly concerned, with crushing and grinding calculations can realize. In developing a new theory it is first necessary to re-examine critically the assumptions underlying

Jan 1, 1952

By Harold A. Krueger

FACILITIES and mining operations of the National Lead Co., St. Louis Smelting and Refining Division, near Fredericktown, Mo., are situated in a famous mining area. Copper, lead, nickel, and cobalt have been mined here for more than 100 years, work having been started on a high sulphide copper outcrop in 1847. Lamotte sandstone is characterized by differential compaction on a rigorously eroded pre-Cambrian surface. The Bonneterre formation was therefore a good host for minerals not generally found in mineable quantities in these midwestern areas. Unusually complex minerals, however, make beneficiation difficult, and because of irregular ore thicknesses and elevations many engineers and operators have not attempted to mine the property. Others have tried who failed. This paper deals with economic, efficient, and competitive methods of mining these highly irregular orebodies, as compared to the open-stope, room-and-pillar methods normally used for horizontal-bedded lead deposits. For the purpose of this study it should be understood that the ore is found in two distinctly different types of occurrences, one to be designated as basin ore and the other as contact ore. Mining of basin ore is complicated by many faults, fractures, cross faults, and breaks. Contact ore is complex because it is found on flanks or slopes of pre-Cambrian knobs or highs. The dip of the mining floor for the latter type varies between 18" and 45". Occurrences of both types of ore are complicated by water courses or solution channels which carry unconsolidated shale, lime, sand, and dolomite. This material is also found between the bedding planes of the members of the Bonneterre formation. The water found where there are fractures, faults, and channels makes it very fluid and tacky, see Fig. 1, particularly after it has been blasted and handled by loading and hauling machines. Much of the ore can be wadded and thrown without dispersing. During early operations by the Buckeye Copper Co. in 1861 and the North American Lead Co. from 1900 to 1910, conventional narrow-gage railroad and side dump mine cars were used with hand shoveling. The complications of mining the contact ore, the only type attempted at this time, can be appreciated when it is realized that operators were obliged to use mules for haulage. Haulageways constructed on these slopes were of necessity similar to wagon trails or goat trails up the side of a mountain. In other words, it was merely a matter of going from side to side of the strike length of the slope, gaining a little in elevation on each shuttle trip. Production totaled only one to two tons per manshift. A few years later, about 1913, the property was purchased by combined Canadian interests known as the Missouri Cobalt Co., and the use of trolley locomotives was initiated. Between 1900 and 1928 a land agent using churn and diamond drilling methods prospected scattered sections of the area. In 1928 the first property was purchased by the present company, then operating as the St. Louis Smelting and Refining Co. Check drilling and prospecting was carried out by the company at various times between 1928 and 1939 to correlate the erratic mineralization. Much information about both types of orebodies was accumulated, but it was still questionable as to whether money should be invested to work these occurrences. In anticipation of high lead and copper prices, about the time World War II started, it was decided to develop and bring into production some of this ore. In 1942 No. 1 shaft was put down on the largest basin-type orebody and in 1943 No. 2 shaft was put down on contact-type ore. Operations were expanded when No. 3 shaft was completed in 1943, and progressed further in 1948, when National Lead Co. dewatered and opened No. 5 and 6 mines, old workings of the North American Lead Co. and the Missouri Cobalt Co. Because of the differential compaction of Lamotte sandstone over the pre-Cambrian porphyry, in some instances mineable thicknesses of basin-type ore occurred 20 to 30 ft above the sand. This is the exception rather than the rule, since most of the mineralization starts at the sand and is variable in thickness. The ore was attacked, therefore, by development drifts and crosscuts at the lowest possible elevation, where the ore immediately overlying the Lamotte sandstone could be drained and made accessible for mining. It was planned to connect to the drifts and crosscuts with raises to mine ore deposited 20 to 30 ft higher. The higher orebodies were thus mined as slusher levels. Slusher hoists were used to drag the ore into the raises, which were made into hoppers. The ore was then loaded into 32x32-in. ore cans, hauled to the shaft by battery locomotives, and hoisted by the conventional Tri-State method. The rate of efficiency was 5 to 6 tons per manshift underground. The contact-type ore was attacked in a similar way, except that the orebodies were not nearly so wide, so that they were more flexible for slusher loading into cans. This advantage was offset, however, by haulage complexities, since the railroad was constructed on steep slopes. Through experience and ingenuity, many improvements were made in mining both types of ores. The two levels, so-called, in the basin-type ore-bodies were connected as previously planned, more efficient locomotives replaced the older ones, and a

Jan 1, 1954

By James Watson Baxter

Fluxes are used to promote pyrometallurgical processes that rely on adhesion (soldering or brazing) or fusion (gas and arc welding) to join metallic surfaces. In the adhesive processes, the metal surfaces to be joined are not melted; the join is formed using a filler metal with lower melting point than the base metal. Fusion welding involves use of heat in excess of the melting point of the base metal. The fused joint may be achieved either by simply fusing together metal surfaces brought in contact with each other or by introducing additional molten metal of similar composition to form a fused joint. ADHESIVE PROCESSES--SOLDERING AND BRAZING In order for molten filler metal, solder or braze, to spread in a manner that creates a successful join; the work surfaces on the base metal must be thoroughly cleansed. Fluxes remove stubborn oxide films and other surface contaminants, promote wetting of the work surfaces, add fluidity to the solder or braze, and enhance workability and ease of spreading. Brazing processes involve higher temperatures than those reached in soldering. Brazing fluxes, which must remain active and effective at the higher temperatures, differ from those employed in soldering. Some common fluxes used in adhesive processes are rosin for soldering tin and electrical connections, hydrochloric acid for use in soldering galvanized iron and other zinc surfaces, and borax for brazing. Soldering and brazing are similar processes, the primary difference being the temperature at which the joining operation is carried out. Soldered joints, produced with low-melting-point fillers (solders) that melt and flow at temperature less that 450°C (Althouse et al., 1988) can sustain loads of 1 to 1.7 MPa for extended periods of time (Anon., 1966). Brazing involves the use of filler materials with melting points commonly above 500°C and generally provides stronger joints than those obtained with solder. Both processes require local application of heat to melt and spread the filler so that the molten filler can wet (adhere to) the base metals by alloying and diffusion. Soldering Soldering is a means of joining metals by adhesion using a metallic bonding alloy as the filler, commonly a mixture of lead and tin. However, the adhesion of solder depends more on its ability to be keyed into minute surface irregularities than on alloying. The most familiar application is to provide and secure electrical connections. Soft solders can range from 1 to 70% tin with the remainder mostly lead. However, for general-purpose, soft-solder work, the alloy is commonly 50% lead-50% tin. Higher lead contents provide a wider range in the melting temperature and, for this reason, a 60% lead-40% tin alloy, which yields a mushy mixture, is used for wiped joints in lead sheet and pipe work. Conversely, 40% lead-60% tin alloys are used in soldering tin and other low- melting-point materials for which a narrower range of melting temperature is required. There are numerous other solder compositions such as tin-silver, 95% tin-5% silver and antimony-tin, 95% tin and 5% antimony (Carlin, Jr., 1992). Heat needed to melt and spread the solders is commonly provided by electrically heated, copper-tipped soldering irons or by means of torches; the solder is applied by hand, usually face-fed by means of wire. For wiped joints in plumbing and lead-cable splicing, the solder is manipulated with cloth pads. The molten solder wets the joint surfaces and is drawn, by surface tension, into minute fissures and capillary openings. Other applications involve use of induction heaters and furnaces with pre-shaped solder appropriately placed prior to fluxing and heating. In some processes, the joints are immersed in molten solder. Constituents and Role of Soldering Fluxes: Soldering fluxes generally fall into one of three categories: highly corrosive fluxes, intermediate fluxes, and noncorrosive fluxes. These same categories are sometimes designated inorganic, organic and rosin-based respectively (Althouse et al., 1988). Common constituents of each group are discussed briefly below. Corrosive Fluxes (Inorganic). Work with aluminum, magnesium, stainless steel, high alloy steel, aluminum bronzes, and silicon bronzes is carried out at temperatures in the upper portion of the range for solder operations. Soldering these materials requires use of highly active, corrosive fluxes to remove and prevent the formation of the especially stubborn, hard, oxide films that form on these materials upon exposure to the atmosphere. The corrosive fluxes consist of inorganic acids and salts that are applied either as pastes or dry. They are active at elevated temperatures and, since they remain active after the soldering is completed, must be completely removed. The main constituent of most corrosive fluxes is zinc chloride with a melting temperature well above the solidus temperature of most commercial tin-lead solders. It is made by the action of hydrochloric acid on zinc. When zinc chloride is used alone, un- melted particles of this corrosive salt get caught up in the joint and weaken it. For this reason, other inorganic salts such as ammonium chloride (NH4Cl) or sodium chloride (NaCl) may be added to lower the melting temperature. A mixture of zinc chloride and ammonium chloride is very effective because the excellent oxide reducing properties of ammonium chloride and the protective action of the molten zinc chloride combine to produce a fluxing action superior to that achieved when either is used alone. In addition to zinc chloride, ammonium chloride, and sodium chloride; common con-

Jan 1, 1994

By Kathleen Kreiss, A. James Ruttenber

INTRODUCTION Early in the morning of July 16, 1979, there was a breach in the earthen retaining dam of a tailings pond at the United Nuclear Corporation&apos;s (UNC&apos;s) Church Rock uranium mill. The acidified liquid and tailings slurry spilled through the damaged portion of the retaining wall into an arroyo that is a tributary to the Rio Puerco river system. The Rio Puerco runs through Gallup, New Mexico, and eventually crosses the New Mexico-Arizona border (Fig. 1). On its way to Gallup, the Rio Puerco and its tributaries pass through land with a checkerboard pattern of ownership, with portions owned or leased by the Navajos, individuals, the Bureau of Land Management, and the State. In terms of tailings liquid volume (3.6 x 108L; 94 million gal), the UNC spill ranks as one of the largest. The mass of solids released in the slurry (10.0 x 105 kg; 1 100 tons) appears to be close to the median for accidents of this kind, however [U.S. Nuclear Regulatory Commission (NRC), 1979]. The UNC first opened its Church Rock uranium mill in 1977 on land adjacent to acreage belonging to the Navajo tribe. The mill, which is next to the UNC Church Rock mine, is located approximately 16 km (10 miles) northeast of Gallup, New Mexico (Fig. 1). Gallup, a town of 18 000 people, is the closest population center. The region surrounding the plant site is sparsely populated by Navajos, at a density of approximately 5.8 persons/km2 (15 persons/sq mile). The UNC mill and mines employ approximately 650 persons, and the adjacent Kerr-McGee uranium mine employs about 300. The UNC mill normally processes 3.2 x 106kg/day (3 500 tons/day) of uranium ore, depositing the acidified tailings slurry in a series of three earthen holding ponds. The tailings ponds are located east of the pipeline arroyo that feeds into the Rio Puerco approximately 2.4 km (1.5 miles) from the southernmost tailings dam. The liquid portion of the tailings slurry evaporates in the ponds; hence, under normal conditions, there is no surface flow from the holding ponds to the arroyo. Both runoff from the plant site after heavy rains and possible seepage from the tailings ponds may deliver radionuclides to the arroyo-river system, however. The dam across the southernmost tailings pond was considered to be in keeping with the state of the art. However, the New Mexico Environmental Improvement Division (NMEID) had warned UNC about dangers of locating the pond over a heterogeneous geological formation. The state Engineer&apos;s Office approved of the site only after UNC agreed to strict design criteria. Others have pointed to dangers of constructing earthen dams for impoundment of uranium mill tailings (Carter, 1978). Causes of the dam break were multiple: the UNC mill filled the tailings pond to a level that exceeded permit criteria; the tailings pond was lined improperly; the dam was constructed using clay that was compacted excessively, resulting in cracking and subsequent seepage; and the unstable substrate beneath the dam permitted differential settling. The UNC Church Rock mine has continuously released dewatering effluent into the pipeline arroyo at a rate of 88.3 L/sec (1 400 gal/min) since 1968. Before 1975 this effluent was not treated; after 1975 it received precipitation treatment for removal of Ra-226. Radionuclides are also released into the river system through the dewatering of the Kerr-McGee uranium mine 1.6 km (1.0 mile) north of the UNC mill. During usual mining operations, approximately 227 L/sec (3 600 gal/min) are released into the pipeline arroyo and subsequently into the Rio Puerco. The Kerr-McGee mine began continuous release of dewatering effluent in January 1972. In 1974 Kerr-McGee began Ra-226 precipitation treatment of its dewatering releases, but NMEID data indicate that treatment has often been incomplete. The effluent from both mines has been responsible for transforming the downstream portion of the Rio Puerco from a sporadically dry riverbed into a continuously flowing stream and has contributed to the current levels of background radiation along the river system (Table 1). This paper will summarize the postspill monitoring efforts and relate the assessment of this spill to the general question of evaluating the health effects of nuclear fuel-cycle wastes. The data pertaining to the measurement of radionuclides in the Church Rock environment and the radionuclide concentrations in animals will appear in forthcoming reports. CHURCH ROCK HEALTH EFFECTS ASSESSMENT APPROACH The initial health effects evaluation involved identifying the radionuclides that were released into the river system from the tailings pond. Table 1 lists the State of New Mexico maximum permissible radionuclide concentrations for liquids released to unrestricted areas, the typical tailings liquid concentrations, and postspill river water concentrations. The tailings liquid contained comparatively high levels of Th-230, Ra-226, Pb-210, and Po-210--all of which, according to postspill river water samples, had exceeded the state maximum permissible concentrations (MPC) at one time or another. After the radionuclides in the tailings were identified, pathways through which humans could be exposed were clarified. Environmental monitoring data were then used to quantify the important pathways of human exposure. Water samples were collected from the river, from test wells dug near

Jan 1, 1981

By R. D. Boddorff, R. L. Ash, C. T. Butler, W. W. Kay

DRILLING and blasting in anthracite open-pit mines is a continuous problem to contractors and explosive engineers because of the diverse conditions caused by the nature of the geological formations, the extensive mining of the portions of coal beds near the surface, and the proximity of many strip pits to populated areas. Pennsylvania anthracite occurs in four separate long and narrow fields totaling only 480 sq miles. The coal measures are rock strata and coal beds that are considerably folded and faulted. The crests of the anticlines are eroded extensively. The beds outcrop on the mountain sides and dip under the valleys. At first only the upper portions of the synclines could be stripped. Now stripping to increasingly greater depths is economically possible, as is indicated by the fact that the proportion of freshly mined anthracite produced by strip mining has increased from 3.7 pct of the total tonnage in 1930 to 29.6 pct in 1950. Much of the rock overlying the deeper beds now being stripped is so extensively broken that considerable difficulty is experienced in drilling satisfactory blast holes and in using explosives in such manner as to insure a uniformly broken material easily removed by the excavating machinery. Such breaking of rock strata has occurred because the bed now being stripped has been mined extensively in former years by underground methods, and tops of gangways and chambers have subsequently failed. Draglines are used to uncover coal where the overburden can be moved with little or no rehandling. These machines range in size from those having a 2 cu yd capacity bucket on a 60-ft boom to those handling a 25 cu yd bucket on a 200-ft boom. Draglines are also used to strip to the bottom of the coal basins if the depth and the distance between the crops are not too great. For this type of operation blast holes are drilled full depth to the bed. These holes are commonly 30 to 90 ft deep; however, in exceptional cases, holes may be as shallow as 12 ft or as deep as 130 ft. Drilling is normally done for blasts of 12,000 to 60,000 cu yd of overburden, 30,000 cu yd being considered an average blast if vibration is not the controlling factor. Where the stripping of wide basins or the exposure of a moderately pitching vein makes the use of draglines impractical, dipper front shovels equipped with 4 to 6 1/2 cu yd buckets load into trucks. Overburden is removed in benches of 25 to 30 ft with blast holes drilled 4 or 5 ft deeper than the planned floor of the bench. For shovels under 5 cu yd bucket capacity the volume blasted varies from 8000 to 12,000 cu yd, whereas a volume of 30,000 to 50,000 cu yd of overburden is frequently blasted at one time for the larger shovels where vibration is not an important factor. During the past decade the churn drill, generally the Model 42-T Bucyrus-Erie blast hole drill equipped for drilling 9-in. diam holes, has become the most common blast hole drilling machine. Electricity powers half the churn drills in use and is preferred on the large strippings where electric shovels are operated and the working area is concentrated. On these operations the cost of additional electricity for the drills is less than the cost of fuel to operate diesel units because of the existing large demand load of the excavating equipment. Moreover, electric motors start more easily in cold weather and generally are less expensive to maintain. Diesel driven units are employed where a higher degree of mobility. is required. The average drilling speed is 8 ft per hr, although in softer rocks a rate of 15 ft per hr is attained. Where rock is hard and strata is badly broken, drill speeds may &apos; be less than 2 ft per hr. Low drilling production results under these circumstances when loose material falling from the upper portion of the drill holes causes drill stems to be jammed. Rock formations vary so greatly in the region that a 9-in. diam churn drill bit may become dull after drilling only 2 ft or may drill satisfactorily for 56 ft; however, an average of 35 ft is usual in sandstone of medium hardness. Dull bits are hoisted to flat bed trucks by the sand line of the drill and are usually sharpened in the contractor&apos;s bit shop adjacent to the job. Care is generally taken to cover the thread end of the bit with a cap. To facilitate handling of bits around the drill, a heavy thread protector having an eye top is becoming more popular than the flat-top rubber or metal cap furnished with new bits. The 9-in. diam blast holes for a 25 to 30 ft bench are normally on 18x18 ft to 20x20 ft spacings, depending on the character of the overburden, although in broken ground 15x18 ft centers may be used to obtain better breakage and a more even bottom for the bench. The patterns of holes for shots

Jan 1, 1952

By M. Metzger, J. C. Bilello

Microyielding in 99.999 pct Cu occuwed in two distinct parabolic microstages and was substantially indeoendent of grain size at the relatiz~ely large grain sizes stzcdied. The strain recouered on unloading was a significant fraction of the forward strain and was initially higher in a copper-coated single crystal than in poly crystals. Results were interpreted in terms of cooperative yielding and short-range dislocation motion activated otter a range of stresses, and a formalism was given for the first microstage. It was suggested that models involving long-range dislocation motion are more appropriate for impure or alloyed fcc metals. THERE are still many unanswered questions concerning the degree and origin of the grain size dependence of plastic properties. In the microstrain region, a theory of the stress-strain curve proposed by Brown and Lukens,&apos; based on an exhaustion hardening model in which the grain boundaries limit the amount of slip per source, accounted for the variation with grain size of microyielding in iron, zinc, and copper.&apos; This theory assumes N dislocation sources per unit volume whose activation stress varies only with grain orientation. Dislocations pile-up against grain boundaries until the back stress deactivates the source, which leads to a relationship between the axial stress and the strain in the microstrain region given by: where G is the shear modulus, D the grain diameter, a the flow stress, and a, is the stress required to activate a source in the most favorably oriented grain.3 If this or other grain-boundary pile-up models are correct, then the reverse strain on unloading would be much larger for a polycrystalline specimen than for a single crystal. Also, the microplasticity would become insensitive to grain size if this could be made larger than the mean dislocation glide path for a single crystal in the microregion. These questions are examined in the present work on polycrys-talline copper and a single crystal coated to provide a synthetic polycrystal. EXPERIMENTAL PROCEDURE Tensile specimens 3 mm sq were prepared from 99.999 pct Cu after a sequence of rolling and vacuum annealing treatments similar to those recommended by Cook and Richards4-6 to minimize preferred orientation. Grain size variation from 0.05 to 0.38 mm was obtained by a final anneal at temperatures from 310" to 700°C. Dislocation etching7 revealed pits on those few grains within 3 deg of (111). For all grain sizes dislocation densities could be estimated as -107 cm per cu cm with no prominent subboundaries. The single crystals, of the same cross section, were grown by the Bridgman technique with axes 8 deg from [Oll] and one face 2 deg from (111). An anneal at 1050°C produced dislocation densities of 2 x 106 cm per cu cm and subboundaries -1 mm apart in these single crystals. A Pb-Sn-Ag creep resistant solder was used to mount the specimens, with a 19 mm effective gage length, into aligned sleeve grips fitted to receive the strain gages. All specimens were chemically polished and rinsed8 to remove surface films just prior to testing. The synthetic polycrystal was made by electroplating a single crystal with 1 µ of polycrystalline copper from a cyanide bath. Mechanical testing was carried out on an Instron machine using two matched LVDT tranducers to measure specimen displacement, the temperature and the measuring circuit being sufficiently stable to yield a strain sensitivity of 5 x 107. At the crosshead speeds employed, plastic strain rates were, above strains of 10¯4, about 10¯5 per sec for polycrystalline specimens and 10-4 per sec for the single crystals. Plastic strain rates were an order of magnitude lower at strains near l0- &apos;. A few checks at strain rates tenfold higher were made for reassurance that the initial yielding of polycrystalline copper was not strongly strain-rate dependent. Test procedures followed the general framework outlined by Roberts and Brown.9,10 An alignment preload of 8 g per sq mm for polycrystals, and 2 to 4 g per sq mm for single crystals, was used for all tests. These gave no detectable permanent strain within the sensitivity of the present experiments; although at these stress levels, small permanent strains are detectable in copper with methods of higher sensitivity.11 12 stress and strain data are reported in terms of axial components. RESULTS General. The initial yielding is shown in the stress vs strain data of Fig. 1. For polycrystals, cycle lc, the loading line bent over gradually without a well-defined proportional limit, and almost all of the plastic prestrain appeared as permanent strain at the end of the cycle. The unloading curve was accurately linear over most of its length with a distinct break indicating the onset of a significant nonelastic reverse strain at the stress o u, indicated by the arrows. The yielding in subsequent cycles, Id and le, had the same general character. The single crystal behavior, shown to a different scale at the right of Fig. 1, was different in that initially the nonlinear reverse strain was unexpectedly much greater than for polycrystals. It should be noted that these soft crystals had a small elastic

Jan 1, 1970

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.&apos;, &apos; Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,&apos; are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952