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By R. H. Edsal, G. Horvay

The transient one-dimensional heat-conduction equation is solved for two semi-infinite media, at different initial temperatures, brought into (poor) thermal contact. It is shown that the two interface temperatures gradually approach the well-known, instantaneously assumed, common interface temperature of the case of zero contact resistance. The present analysis, with slight modifications, may be used in fair approximation also for the class of problems involving a change of phase. One particular application of the boundary value problem solved in this paper concerns the determination of the temerature distribution in metal castings and molds.P This problem has been treated extensively by analytical methods (see e.g., the literature listed in Refs. 1 to 4) by electrical analogs (see e.g., Refs. 11 to 14) and also by experimental methods (see the literature listed in Refs. 4, 5), but prior to the work of Pellini and Ruddle the experimental results were rather unreliable. Immediate motivation for the work described in this paper was to better understand the results of Pellini,' which are typified by the curves of Fig. 1. Pellini cast 20-in. high, 7-in. sq steel ingots into cast-iron molds of various thicknesses. He measured the temperatures at mid-height, at a number of stations in the casting and the mold, and obtained the cooling curves shown in Fig. 1. The most conspicuous thing about Fig. 1 is the large temperature discontinuity at the interface between casting and mold, due presumably to the shrinking away of the casting from the wall and the attendant creation of an airgap, as the casting cools. Such a contact resistance slows down the anticipated freezing rate; an analytical prediction of this is of much interest in foundry practice. The determination of the effect of contact resistance in the presence of a change of phase will be dealt with, by an approximate method, in a separate paper.' In the present paper the much simpler problem is considered in which there is contact resistance but no change of phase. This problem frequently arises in the analysis of aircraft structures.+ It can initial temperature, and may be regarded as semi-infinite. We suppose the thermal properties in the two media to be time, temperature, and space independent; there are no sources or sinks within the media. In Fig. 2(a) we illustrate, schematically, the case of no contact resistance. The semi-infinite media "0" and "2:' initially at temperatures 8 (- m) and 8(+ -), respectively, are brought into contact at time t =0. A common interface temperature 8,i = is instantaneously established, and thereafter remains constant. Temperature curves are drawn for three instants of time. When there is contact resistance between the two media, the temperature equalization occurs as sketched in Fig. 2(b). Fig. 2(c) illustrates a temperature curve, using the dimension-less notation Barber-Weiner-Boley6 have stated the equations [23a, b] given below, which govern the heat transfer in the two media, and solved them for a rather complicated special case. In their example both media "O" and "2" are finite, are insulated at their far ends, and there is steady heat input into medium 2. In Eq. [27] we give the general solution of the most important special case, where the two media are semi-infinite and there are no sources or sinks. In this case the results may be stated in simple closed form. In Fig. 3, to be discussed in the next section, we illustrate the variation of the interface temperature when steel at 2760" is brought into contact with iron at 100". This example, if we disregard the effect of the heat of fusion, is comparable to Pellini's experimental results, Fig. 1. (Unfortunately, however, experimental determination of the interface temperatures was difficult to carry out, and hence Fig. 1 is not very accurate near the interface.) In Figs. 4 and 5 of the following section, we similarly compare Pellini's sandcasting tests with analytical results for the case where steel at 2760" is brought into contact with sand at 100". It will be pointed out that, insofar as the interface temperatures are concerned, heat of fusion has a minor effect, and so the present approximation, with small modifications, may be

Jan 1, 1961

By D. M. McFarland

A FEW years ago a novel electric detonator known as the split-second or millisecond delay electric blasting cap was introduced for use in quarry blasting. Regular electric blasting caps fired in series may be depended upon to fire within a millisecond or so from the first to the last in a series. Regular delay electric blasting caps are provided that fire one period after the other period in intervals of 1/2 to possibly 11/2 sec. Most split-second or millisecond delays are designed to fire one period after the other period in possibly 25 to 50 millisecond intervals. The ear is not capable of detecting time intervals of this magnitude. The primary thought at the time millisecond delays were introduced was to investigate the results on rock breakage by firing a line of holes in a quarry face so that charges in adjacent holes would not be detonated simultaneously. This could not be accomplished satisfactorily with regular delays. The time interval between successive periods of 1/2 to 1 sec was sufficient to permit considerable movement of the burden. If the burden of one hole was reduced to a great extent by the firing of an adjacent hole, the firing of the hole with the reduced burden would likely reveal this lack of confinement by a terrific report and wild throw of rock. In the early blasts with millisecond delays it was observed that instead of the usual sharp report, the blast had a muffled sound and vibration was not as perceptible as when simultaneous firing was used. Because many quarry operators were being threatened with injunctions or suits for damages by neighbors who claimed structural damage to their buildings, millisecond delays were tried extensively in quarries. In the majority of these trials, the results were very satisfactory. The seismologists recorded the ground movement created by many blasts and verified the initial observations that millisecond delays could be used to reduce vibrations appreciably. In the past few years the advantages of this principle of nonsimultaneous firing of the charges in blasts has become generally accepted. Today the quarry operator who has vibration troubles, inadequate breakage, and excessive backbreak and has not investigated the possibilities of millisecond delay blasting is ignoring a remedy that has proved satisfactory for many. His complacency may be costing him money. Because of the results attained in quarry blasting, it was logical that millisecond delays should be tried in construction work such as in road cuts. As formations in this type of work are likely to change rapidly with advance of the cut, it is more difficult to evaluate results than in quarry blasting. However, this improved control over timing has been beneficial in limiting throw, promoting fragmentation, and reducing overbreak. In blasting near buildings the reduction in vibration and in throw has been especially helpful. As blasters employed in construction work learn what may be accomplished by closer control over the time of firing of explosives charges, more and more millisecond delays are being used to supplant instantaneous electric blasting caps. Improved Fragmentation Underground With this background of promising results, it was not surprising that millisecond delays should go underground. In limestone mining use of millisecond delays as compared with use of cap and fuse or electric blasting caps showed improved fragmentation in stopes and in slabbing operations. Then an opportunity developed to use millisecond delays in some tunnels being driven in a limestone mine (fig. 1). Using the normal charge employed and merely substituting three millisecond delay periods for three regular delay periods, there was a noticeable difference in the appearance and the position of the pile of rock after a blast. A greater portion of the face was exposed, the crest of the pile was farther from the face, and the pile was heaped high along the center line of the tunnel leaving room to walk along the ribs to the face. Fragmentation was appreciably increased. It gave the impression that the slabs had been thrown against each other with tremendous force, promoting the movement of the broken rock along the center line of the tunnel away from the face. Because the drilling and the charge weights were unchanged, the evidence was convincing that the difference in timing was responsible for the difference in results. Probably a greater portion of the energy from the explosives had been expended in doing useful work on the rock. Zeros followed by two periods of millisecond delays were used in the V cut and in two slabs to either side of the cut in this simple round. When millisecond delays, substituted period for period for regular delays, are first tried in a drift round in a mine, and the usual charge of explosives

Jan 1, 1951

By J. H. Swisher

The solubility of graphite in CaO-S2O2-Al,O3 slags was measured by equilibrating slag samples with graphite crucibles and CO gas. Carbon contents as high as 2 ut pct were obtained in CaO-saturated, CaO-A1,O3 slags, and 1.3 wt pct in slags of the composition CaO.Si0,. Although the observed conditions for Sic formation were in agreement with those predicted from thermodynamic data, CaC, was found to form at a lower temperature than predicted frotn thermodynamic data. From measurements of the equilibrium carbon content as a function of CO Partial pressure, it was found that carbide ions dissolve in CaO-A12O3 melts with a valence of minus two. The carbon content increased with CaO concentration in Ca0-Al,O3 melts and increased with SiO, content along the CaO'AlO3-CaOSi0 join in the ternary system. When solid CaC2 was added to CaO-A12O3 and CaO-SiO2-A12O3 slags, it was found that one of the oxides in the slag was reduced by the carbide (Al2O3 in the forrner and SiOz in the latter). In electric furnace steelmaking, a double-slag practice is frequently used to meet alloy specifications. Initially a flush slag, which is oxidizing in nature, is used to remove phosphorus and carbon from the steel bath. Later in the refining period, the flush slag is replaced by a highly reducing carbidic slag. When calcium carbide is formed in or added to a finishing slag, the slag is effective as a desulfurizing agent and also permits alloying elements such as chromium, vanadium, and tungsten to be added to the slag in the form of oxides. The oxides are readily reduced by calcium carbide, thereby minimizing the use of expensive ferroalloys. More work has been done on the thermodynamics of silicon carbide in slags than on calcium carbide. Baird and alor' and Kay and alor' determined the free energy of formation of Sic by measuring the partial pressure of CO in equilibrium with solid silica, silicon carbide, and graphite. Using a similar technique, they determined SiOz activities in CaO-SiOz and Ca0-Si0,-A1203 slags. Rein and chipman3 also determined the free energy of formation of Sic using slag-metal equilibrium measurements. A literature survey has uncovered only one experimental study of the behavior of CaC, in slag systems. Shanahan and cooke4 report the results of some preliminary experiments on the solubility and stability of CaC, in a CaO-A1,03 and a Ca0-Si0-A1,03 slag at a temperature of about 1500". The carbon solubility as CaC, in a slag containing 50 pct CaO and 50 pct A1203 was reported to be 0.6 pct. They also review earlier work on the binary CaO-CaC, system. A eutectic exists in this system, but various investigators disagree on the eutectic temperature and composition. eal has given an explanation for carbide furnace erruptions in terms of the thermodynamic properties of CaC,; his analysis is not based on experimental data, but on compiled data for the free energies of formation of CaC, and CO.' , These data for steel-making temperatures are all extrapolated from the results of low-temperature measurements. In the experiments described in this paper, slag samples were equilibrated with graphite crucibles and with mixtures of CO and argon or with CO gas at 1 atm total pressure for measurement of the carbon solubility. Most of the work was done on Ca0-A1203 binary slags, although in some experiments CaO-SiO, and Ca0-Si0,-A1,03 slags were used. EXPERIMENTAL Slag samples of the desired composition for the solubility measurements were obtained by blending pre-fused master slags. The master slags were prepared by fusing mixtures of reagent-grade CaC03 with either A1,03 or Si0, in a graphite crucible. The master slags were crushed, then decarburized in air in a muffle furnace at 1200O C. A schematic diagram of the apparatus is shown in Fig. 1. The source of carbon for the solubility meas-

Jan 1, 1969

By James K. Hallenburg

INTRODUCTION The delayed fission neutron, or DFN technique for uranium ore body analysis uses the first down-hole method for detecting uranium in place quantitatively. This technique detects the presence of and measures the amount of uranium in the formation. DFN TECHNIQUE DESCRIPTION The DFN technique depends upon inducing a fission reaction in the formation uranium with neutrons, resulting in an anomalous and quantitative return of neutrons from the uranium. Since there are no free, natural neutrons in formation, a good, low noise assessment may be made. There are several methods available for determining uranium quantity in situ. The method used by Century uses an electrical source of neutrons. This is a linear accelerator which bombards a tritium target with high velocity deuterium ions. The resulting reaction emits high energy neutrons which diffuse into the surrounding formation. They lose most of their energy until they come to thermal equilibrium with the formation. Upon encountering a fissile material, such as uranium, these thermal neutrons will react with the material. These reactions produce additional neutrons, the number of which is a function of the number of original neutrons and the amount of fissile material exposed. The particular source used, the linear accelerator, has several distinct advantages over other types of sources: 1. It can be turned off. Thus, it does not constitute a radioactive hazard when it is not in use. 2. It can be gated on in short bursts (6 to 8 microseconds). This results in measurements free of a high background of primary neutrons. 3. The output can be controlled. Thus, the neutron output can be made the same in a number of tools, easily and automatically. There are several interesting reactions which take place during the lifetime of the neutrons around the source. During the slowing down or moderating process the neutron can react with several elements. One of these is oxygen 17. This results in a background level of neutrons in any of the measurements which must be accounted for in any interpretation technique. These elements are usually uninteresting economically. The high energy neutrons will also react with uranium 238. However, the proportions of uranium 235 and 238 are nearly constant. Therefore, this reaction aids detection of uranium mineral and need not be seperated out. Upon reaching thermal energy the neutrons will react with any fissile material, uranium 235, uranium 234, and thorium 232. At present, we do not have good techniques for seperating out the reaction products of uranium 234 and thorium 232. However, uranium 234 is a small (.0055%) percentage of the uranium mineral and thorium 232 is usually not present in sedimentary deposits. When the uranium 235 reacts with thermal neutrons it breaks into two or more fragments and some neutrons. This occurs within a few microseconds after the primary neutrons have moderated and is the prompt reaction. One system uses this; the PFN or prompt fission neutron technique. We don't use this method because the neutron population is low and, therefore, the signal is small and difficult to work with, accurately. Within a few microseconds to several seconds the fission fragments also decay with the emmission of additional neutrons. Now, with a long time period available and a large neutron population we gate off the generator and measure the delayed fission neutrons after a waiting period. These neutrons can be a measure of the amount of uranium present around the probe. Thermal neutrons are detected with the DFN technique instead of capture gamma rays to avoid some of the returns from other elements than uranium. LOGGING TECHNIQUE The exact logging technique will depend, to some extent, upon the purpose of the measurement. However, the general technique is to first run the standard logs. These will include: 1. The gamma ray log for initial evaluation of the mineral body and for determining the position of the borehole within the mineral body, 2. The resistance or resistivity log for determining the formation quality, lithology, and porosity. 3. The S. P. curve for estimating the redox state and shale content, and measuring formation water salinity, 4. The hole deviation for locating the position, depth, and thickness of the mineral (and other formations), and 5. The neutron porosity curve. The neutron porosity curve is most important to the interpretation of the DFN readings. The neutrons from this tool are affected in the same way by bore hole and formation fluids as the DFN neutrons are. Therefore, we can use this curve to determine effect of the oxygen 17 in the water. Of course, this curve can be used to determine formation porosity. It can also be used to calculate formation density.

Jan 1, 1979

By T. L. Chu, G. A. Gruber

Silica films hare been rleposited 011 silicon substmtes at 400° to 600°C by a chemical-transport technique using hydrogen fluoride as the transport agent ill a closed system. This transport takes place from a source materia1 1071: temperature to substrates at higher temperatures, as indicated by the thermochemistry of the transport reaction. The experimental variables of- the transport process, such as the substrate temperature, the pressure pi the transport agent, and so forth, have been studied. The rate -determining step of the transport process appears to he the ),ale of chemical reaction in the source region. The transported films are similar to thermally grown silica films in physical proper-ties with the exception of 'some what higher dissolrrtion rates. SILICA films deposited on suitable substrates serve many purposes in electronic devices. They are used for the fabrication of tunneling devices, the surface passivation of devices, and the shielding of devices from nuclear radiation: and as selective masks against the diffusion of specific impurities into semiconductors. Doped silica films can also be used as sources for the diffusion of impurities into semiconductors. Several oxidation and deposition techniques for the preparation of silica films have been developed to meet the requirements of these applications. The therma1 oxidation of silicon by oxygen or steam at temperatures above 900 C is commonly used in silicon technology. The deposition techniques are perhaps more advantageous since they usually require lower temperatures and are not limited to silicon substrates. Silica films have been deposited on silicon and other substrates by reactive sputtering and chemical reactions. The sputtering of silicon in an oxygen atmosphere is capable of depositing good-quality silica films on silicon' and gallium arenide. Many chemical reactions are known to yield silica at room temperature or higher. These reactions may involve intermediate steps. However, the final step yielding silica should take place predominately on the substrate surface in order to produce adherent films. When silica is formed in the gas phase by volume reactions, no adherent deposit can be obtained. Generally, the experimental conditions of a reaction can be varied so that the surface reaction predominates over the volume reaction. The chemical reactions which have been used successfully for the deposition of silica films are briefly as follows. The pyrolysis of alkoxysilanes in an inert atmosphere or under reduced pressure has been employed to deposit silica films on germanium3 and silicon4 at 650" to 750°C in a flow system. The deposition of silica films from alkoxysilanes has also been achieved at nearly room temperature by a low-pressure plasma. Device quality silica films have been deposited on germanium and gallium arsenide by the deposition of an amorphous thin silicon film followed by oxidation at 600" to 700" . Silica films for high-temperature capacitors have been produced by the hydrolysis of silicon tetrabromide at 950°C in argon and hydrogen atmospheres.7 We have developed a chemical-transport technique for the deposition of silica films on semiconductor substrates at relatively low temperatures. The thermochemistry of the transport reaction, the experimental variables of the transport process, and the properties of the transported silica films are described in this paper. THERMOCHEMICAL CONSDERATIONS The transport of solid substances by chemical reactions in the presence of a temperature gradient has been used for the preparation of films and crystals of many electronic materials. In this technique, a gaseous reagent is chosen so that it reacts reversibly with the solid substance under consideration to form volatile products. Since the equilibrium constants of most reactions are temperature-dependent, the transport of these products to regions of suitable temperature in the reaction system would cause the reverse reaction to take place. depositing the original solid. When the equilibrium is shifted toward the formation of the solid as the temperature is decreased, the solid is transported from a high-temperature zone to a lower-temperature region, and vice versa. This chemical-transport technique can be carried out in a closed or gas-flow system. In a closed system, chemical equilibrium is presumably established in the different temperature regions of the system, and the transport agent regenerated in the deposition region repeats the transport process in a cyclic manner. The local chemical equilibrium may not be approached in a flow system: however, this system offers a greater degree of flexibility. Silica reacts reversibly with hydrogen fluoride and this reaction was chosen for the transport process. The over-all reaction between silica and hydrogen fluoride may be written as: SiO2(s) + 4HF(g-) = SiF4Ur) + 2H2O(^)

Jan 1, 1965

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors' reply)— -Williams' arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams' model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams' model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams' strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams' model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By D. M. McFarland

A FEW years ago a novel electric detonator known as the split-second or millisecond delay electric blasting cap was introduced for use in quarry blasting. Regular electric blasting caps fired in series may be depended upon to fire within a millisecond or so from the first to the last in a series. Regular delay electric blasting caps are provided that fire one period after the other period in intervals of 1/2 to possibly 11/2 sec. Most split-second or millisecond delays are designed to fire one period after the other period in possibly 25 to 50 millisecond intervals. The ear is not capable of detecting time intervals of this magnitude. The primary thought at the time millisecond delays were introduced was to investigate the results on rock breakage by firing a line of holes in a quarry face so that charges in adjacent holes would not be detonated simultaneously. This could not be accomplished satisfactorily with regular delays. The time interval between successive periods of 1/2 to 1 sec was sufficient to permit considerable movement of the burden. If the burden of one hole was reduced to a great extent by the firing of an adjacent hole, the firing of the hole with the reduced burden would likely reveal this lack of confinement by a terrific report and wild throw of rock. In the early blasts with millisecond delays it was observed that instead of the usual sharp report, the blast had a muffled sound and vibration was not as perceptible as when simultaneous firing was used. Because many quarry operators were being threatened with injunctions or suits for damages by neighbors who claimed structural damage to their buildings, millisecond delays were tried extensively in quarries. In the majority of these trials, the results were very satisfactory. The seismologists recorded the ground movement created by many blasts and verified the initial observations that millisecond delays could be used to reduce vibrations appreciably. In the past few years the advantages of this principle of nonsimultaneous firing of the charges in blasts has become generally accepted. Today the quarry operator who has vibration troubles, inadequate breakage, and excessive backbreak and has not investigated the possibilities of millisecond delay blasting is ignoring a remedy that has proved satisfactory for many. His complacency may be costing him money. Because of the results attained in quarry blasting, it was logical that millisecond delays should be tried in construction work such as in road cuts. As formations in this type of work are likely to change rapidly with advance of the cut, it is more difficult to evaluate results than in quarry blasting. However, this improved control over timing has been beneficial in limiting throw, promoting fragmentation, and reducing overbreak. In blasting near buildings the reduction in vibration and in throw has been especially helpful. As blasters employed in construction work learn what may be accomplished by closer control over the time of firing of explosives charges, more and more millisecond delays are being used to supplant instantaneous electric blasting caps. Improved Fragmentation Underground With this background of promising results, it was not surprising that millisecond delays should go underground. In limestone mining use of millisecond delays as compared with use of cap and fuse or electric blasting caps showed improved fragmentation in stopes and in slabbing operations. Then an opportunity developed to use millisecond delays in some tunnels being driven in a limestone mine (fig. 1). Using the normal charge employed and merely substituting three millisecond delay periods for three regular delay periods, there was a noticeable difference in the appearance and the position of the pile of rock after a blast. A greater portion of the face was exposed, the crest of the pile was farther from the face, and the pile was heaped high along the center line of the tunnel leaving room to walk along the ribs to the face. Fragmentation was appreciably increased. It gave the impression that the slabs had been thrown against each other with tremendous force, promoting the movement of the broken rock along the center line of the tunnel away from the face. Because the drilling and the charge weights were unchanged, the evidence was convincing that the difference in timing was responsible for the difference in results. Probably a greater portion of the energy from the explosives had been expended in doing useful work on the rock. Zeros followed by two periods of millisecond delays were used in the V cut and in two slabs to either side of the cut in this simple round. When millisecond delays, substituted period for period for regular delays, are first tried in a drift round in a mine, and the usual charge of explosives

Jan 1, 1951

By E. M. Porbansky

DURING the investigation of the electrical transport properties of copper, it became necessary to prepare large single crystals of the highest obtainable purity. In an effort to meet these demands, single crystals of copper have been grown by the conventional pulling technique—as has been used for the growth of germanium and silicon crystals.' Low-temperature resistance measurements made on these crystals show that, as far as their electrical properties are concerned, they are generally of significantly higher purity than the original high-purity material. The use of these pure single crystals with very high resistance ratios has made possible the acquisition of detailed information regarding the electron energy band structure of copper2-' and has stimulated widespread effort on Fermi surface studies of a number of other pure metals. It is the purpose of this note to describe our method of preparing very pure copper crystals by the Czochralski technique. Precautions were taken to prevent contamination of the melt from the crystal growing apparatus. A new fused silica growing chamber was used to prevent possible contamination from previous groqths of other materials such as germanium, silicon, and so forth. A new high-purity graphite crucible was used to contain the melt. This crucible was baked out in a hydrogen atmosphere at -1200°C for an hour, prior to its use in crystal growth. Commercial tank helium, containing uncontrolled traces of oxygen, was used as the protective atmosphere. A trace of oxygen in the atmosphere appears to be necessary for obtaining high-purity copper single crystals. A 3/8-in-diam polycrystalline copper rod of the same purity as the melt was used as a seed. The copper rod was allowed to come in contact with the melt while rotating at 57 rpm. When an equilibrium was observed between the melt and the seed (that is, the seed neither grew nor melted), the seed was pulled away from the melt at a rate of 0.5 mils per sec. As the seed was raised, the melt temperature was slowly increased, so that the grown material diminished in diameter with increasing length. When this portion of the grown crystal was -1 in. long and the diameter reduced to less than 1/8 in., the melt was slowly cooled and the crystal was allowed to increase to - 1-1/4 in. diam as it was grown. By reducing the diameter of the crystal in this manner, the number of crystals at the liquid-solid interface was decreased until only one crystal remained. Fig. 1 shows a typical pulled copper single crystal. The purity of the starting material and the crystals was determined by the resistance ratio method: where the ratio is taken as R273ok/R4.2ok. The starting material, obtained from American Smelting and Refining Co., was the purest copper available. Most of the pulled copper crystals had much higher resistance ratios than the starting material. The highest ratio obtained to data is 8000. Table I is an example of the data obtained from some of the copper crystals. Note that Crystal No. 126 had a lower resistance ratio than its starting material and this might be due to carbon in the melt. The melt of this crystal was heated 250" to 300°C above the melting point of copper. At this temperature it was observed that copper dissolved appreciable amounts of carbon. The possible presence of carbon at the interface between the liquid and the crystal will result in reducing conditions and negate the slight oxidizing condition required for high purity as discussed below. The possible explanations of the improvement in the copper purity compared to the starting material are: improvement in crystal perfection, segregation, and oxidation of impurities. Of these, the latter seems to be most probable. A study of the etch pits in the pulled crystals showed them to have between 107 and 108 pits per sq cm. The etch procedure used was developed by Love11 and Wernick.10 The resistivity of the purest copper crystal grown was 2 x 10-10 ohm-cm at 4.2oK; from the work of H. G. vanBuren,11 the resistivity due to the dislocations would be approximately 10-l3 ohm-cm, which indicates that. the dislocations in the copper crystals would contribute relatively little to the resistivity of the crystals at this purity level. Segregation does not seem likely as the reason for purification of the material, since the resistivity of the first-to-freeze and the last-to-freeze portions are approximately the same, as was observed on Crystal No. 124. On most of the crystals that were examined, the entire melt was grown into a single crystal. If the

Jan 1, 1964

By B. D. Cullity, K. S. Sree Harsha

When a copper or aluminum single crystal is swaged into wire, the resulting deformation texture depends on the original orientation of the crystal. The<100> and <111>orientations me essentially stable, while <110> is unstable. The greater the <100> content of the deformation texture, the stronger the wire is in torsion. the greater the<111>content, the stvonger it is in tenszotz. The preferred orientation (texture) of fcc wires, either after deformation or recrystallization, is usually a double fiber texture in which some grains have <100> parallel to the wire axis and others have <111>. The relative amounts of these two texture components, as reported by different investigators for the same metal, vary considerably. Previous work in this laboratory&apos; has shown that the starting texture of a wire, i.e., the texture which it has before deformation, can have a decided influence on the texture produced by deformation. In particular, it was found that the deformation texture of copper wire is essentially a single <100> texture, if the wire before deformation contains only a <100> component. This is true even when the deformation is carried to more than 98 pct reduction in area. This paper reports on further studies of the role played by the starting texture. Copper and aluminum single crystals of various orientations have been cold swaged into wire, and quantitative measurements of the resulting deformation textures have been made. The tensile and torsional properties of the deformed wires have also been measured, and the relation between these properties has been correlated with the texture of the wire. These measurements were made in order to demonstrate that a cold-worked wire can be made relatively strong in torsion and weak in tension, or vice versa, by proper selection of the texture before deformation. MATERIALS The copper was of the tough-pitch variety, containing, by weight, 99.962 pct Cu, 0.003 pct Fe, 0.025 pct 0, and 0.0021 pct Si. The aluminum contained more than 99.99 pct .&apos;41; the only reported impurities were 0.001 pct Fe, 0.001 pct Si, and 0.003 pct Zn, by weight. Large single crystals of these metals were grown by the Bridgman method in graphite crucibles and a helium atmospliere. Cylindrical specimens of predetermined orientation, about 1.5 in. long and 0.36 in. in diameter, were machined from the as-grown crystals and then etched to 0.25 in. to remove the effects of machining. Their orientations were checked by back-reflection Laue photographs, and they were then swaged to a diameter of 0.050 in. (96 pct reduction in area). 111 order to study the "inside texture" of the deformed wires, they were etched, after swaging, to a diameter of 0.040 in. before the texture measurements were made. TEXTURE MEASUREMENTS The fiber texture which exists in wire or rod can be represented by a curve showing the relation between the pole density I, for some selected crystal-lographic plane, and the angle $ between the pole of that plane and the wire axis (fiber axis). Such a curve will show maxima at particular values of , and these values disclose the texture components which are present. The relative amounts of these components can be determined2&apos;3 from the areas under the maxima on a curve of I sin F vs F. It is seldom necesszlry to measure I over the whole range of F from 0 to 90 deg, since the existence of maxima in the low-F relgion can be inferred from measurements confined to the high-F region. The X-ray measurements were made with a General Electric XRD-5 diffractometer and filtered copper radiation, according to one or the other of the following procedures: 1) A method developed in this laboratory,4 involving diffraction from a single piece of wire. 2) A modification of the Field and Merchant method.5 This method was originally devised for the examination of sheet specimens, but it can easily be adapted to the measurement of fiber texture. Three or four short lengths of wire are held in grooves machined in the flat face of a special lucite specimen holder. The axes of the wires are parallel to the plane defined by the incident and diffracted X-ray beams, and the holder to which the wires are attached can be rotated step-wise about the diffractometer axis for measurements at various angles 9.

Jan 1, 1962

By Robert L. Akre

When Marco Polo visited China in the 13th century, no one knew what black powder was except the Chinese; they knew enough to make dazzling fireworks with it. But the realization that black powder could also do useful work came much later and, like all important discoveries, it altered the course of history. It was in the 14th century that black powder was first used to break rock in a very crude way; there were no drills and the powder was simply poured into cracks and exploded by setting it afire. Because its energy value was pretty low, the need for something more powerful was felt when the industrial revolution began. In the 1850s, miners began experimenting with liquid nitroglycerine on a limited scale. This was a very sensitive and dangerous explosive. Fortunately in the 1860s, Alfred Nobel succeeded in stabilizing nitroglycerine by absorbing it in kieselguhr-and a new product, dynamite, was born. With it, miners were able to unleash the great energy of nitroglycerine for blasting purposes. But dynamite was still a very sensitive explosive. In subsequent years, other explosives of various strengths and characteristics were developed, such as blasting gelatin, gelatin dynamite, ammonia dynamites, (all containing some nitroglycerine or nitrostarch), and liquid oxygen explosives. These products and their variations supplied the blasting trade for many years. A grained ammonium nitrate product containing some carbonaceous material entered the market in the 1930s. This explosive had below-zero sensitivity-meaning: a No. 6 blasting cap imbedded in it would not detonate it. A more sensitive initiator, called a primer, was needed to detonate this mixture. From Rags to Primacord to Solid-State The first initiator for an explosive charge was probably a rag slowly burning its way to the charge; this method was quite unreliable. Then came the burning fuse, which was an improvement. Next was the nonelectric blasting cap initiated by a fuse. With these initiators, a miner needed quick reflexes and good legs; upon lighting the fuse, he had to run immediately for cover. Development of the electric blasting cap that allowed for accurate timing eliminated this hazard; the electric cap, however, introduced other safety problems because of its susceptibility to extraneous electricity, e.g., ground currents, lightning, and static electricity. These caps also became available in millisecond delays. Development in the mid-1930s of Primacord, a detonating fuse insensitive to electrical currents or impact, further reduced blasting hazards, and is generally acknowledged as the safest known means of initiation. Eventually, Primacord millisecond connectors also became available for delay patterns in blasting. In the mid-1960s, the Primadet delay was introduced; it is a practical nonelectric detonator system that offers the precise timing of electric blasting caps-and is immune to the hazards or effects of extraneous electricity. Recently, Research Energy of Ohio, Inc. introduced a new type of solid-state blasting machine that combines a sequential timer and delay caps. It enables the efficient breakage of rock with a minimum amount of shock, ground vibration, and noise. Improvements in Blast-Hole Drilling World War II created an enormous demand for coal and other minerals in the U.S. and elsewhere. Great efforts and large amounts of capital were spent to find new mineral deposits and develop better mining methods. But while mechanization in mining proceeded at a rapid pace particularly in open-cut work, there was a definite lag in developing new or improved machines for drilling blast holes. The industry continued to depend largely on horizontal, churn, and pneumatic drills. No better machine was available for large scale production. The need for improvement in this phase of mining became more acute in the post-war years. Despite efforts toward further mechanization, mining costs rose rapidly because of mounting inflation and increasingly high wages. In most operations, drilling and blasting the overburden became the principal item of cost. Therefore, whatever size holes were being drilled, the holes had to be spaced so that any foot of the bore hole could be loaded with the maximum load required for the number of cubic yards of material that each foot of the hole was carrying. With the smaller holes that were being drilled, the proportion of drilling cost to the total drilling and shooting cost was much higher than it would have been with larger holes (because of the closer spacing required by smal-

Jan 1, 1977

By G. F. Leaming

The paper by R.V. Ramani and R.J. Sweigard is a wonderful description of the labyrinthine web that has been spun about the mining industry by energetic bureaucrats and politicians over the past 50 years. The remedy for the problem, however, is not more of the same, but less. That may be difficult for the industry to achieve, for it is not a technical solution but a political one. And the current fervor for more detailed planning at all levels of government and private enterprise has become deeply ingrained. The authors recommend the provision of more information about mining and mineral resources to "macro" (i.e., government) land use planners. They apparently overlook, however, the already strong tendency on the part of most government land use planners to consider themselves omniscient. Thus, giving them more information about the technical problems of mining will only make them want to get more and more involved in the "micro" (private, site specific) mine development and production plans of the individual mining firm. In fact, this has already happened at all levels of jurisdiction from municipal to federal government. Examples are legion. The most effective way to ameliorate the adverse impacts of government land use planning on existing and potential mining operations is to: (1) introduce greater flexibility in the definition of land use zones by local and state governments; (2) adopt realistic and relevant ambient environmental performance standards in governing relationships between mineral land uses and concurrent or subsequent nonmining land uses; (3) allow greater leeway for economic considerations in land use decisions in contrast to the explicit legalistic approach now in vogue; (4) recognize that all minerals are not the same and that sand and gravel mining should not be treated the same as underground metal mining, coal stripping, oil field production, or in situ leaching; and (5) eliminate the notion that mining operators should be responsible for determining in detail the use of land by subsequent owners of mined land. This last bit of conventional ethic really makes no more sense than requiring the builders of every shopping center or government office complex to provide detailed plans for the use of that land when its use for shopping or government is ended. Did the builder of Ebbetts Field plan for Brooklyn after the Dodgers went to Los Angeles? Should the developer of the Bingham Pit plan for suburban Salt Lake City after the copper mining goes to Chile? The nation&apos;s mining industry must address these questions before further bankrupting itself to provide more data to planners and spending thousands of dollars per acre to create land that when reclaimed is worth only a few hundred dollars per acre. ? Reply by R.V. Ramani and R.J. Sweigard We thank Mr. Learning for his valuable contribution. His views on the problems of land use planning and mineral resources are most welcome additions to our paper. As the title indicates, our paper was more concerned with the impacts of land use planning on mineral resource conservation than with the details of the planning process. On the whole, his five recommendations would be helpful for mineral resource conservation. However, we would suggest that the argument he presents for his final recommendation does not address the differences between mining as a land use and commercial or institutional uses. We believe that this difference is the crux of the issue. We share Mr. Learning&apos;s desire to ameliorate the adverse impacts of land use planning. Possibly the most detrimental impact is the loss of mineral resources. Any development, whether mineral or community, that does not give proper consideration to other resources can result in permanent loss or sterilization of resources. With proper planning, some of these losses can be avoided. As our paper indicated, one factor that limits the consideration of mineral resources, and ultimately leads to their sterilization, is the generally inadequate levels of resource characterization and understanding of the unique nature of mineral resources and mining operations. The last point raised by Mr. Learning is also important. In terms of reclamation and land use planning in mining districts, we certainly do not advocate spending more than what the results are worth. The main thrust of the paper was to explore the avenues for conserving the mineral resources so that, at some appropriate time, the issue of mining and reclamation can still be addressed. ?

Jan 1, 1986

By Jr. F. M. Perkins.

Capillary forces play a controlling role in water-drive displacement processes both in laboratory experiments and in actual reservoirs, but their quantitative importance may be quite different in the two cases. Because of the importance of conducting laboratory experiments which are representative of field conditions, it is necessary to understand exactly the role of capillary forces in the displacement process. Though a number of experimental investigations related to this subject are contained in the literature, there appears to be a lack of information pertaining to unsteady-state experiments in water-wet media. This experimental study was conducted to obtain additional laboratory data to clarify further the role of capillary forces in both the macroscopic and microscopic flow of oil and water in porous materials. THEORETICAL CONSlDERATlONS The capillary pressure is defined as the difference in pressure between a continuous oil phase and a continuous water phase in a porous material.&apos; The magnitude of this pressure difference depends on the interfacial curvature and the interfacial tension. The interfacial curvature is determined by the geometry of the pore spaces, the wettability of the rock surfaces, and the quantity of cach phase present. Capillary forces are involved in a water-drive displacement process in that they exert a controlling influence on the microscopic fluid distribution which in turn is reflected in the saturation or macroscopic flow behavior. Microscopic Fluid Distribution Because of the microscopic nature of the displacement of oil by water, it is necessary to consider the flow and the fluid distribution in individual pores. On this microscopic scale the capillary Forces, which act over a distance of one or two sand grain diameters, control the distribution of oil and water under static equilibrium conditions. When an external force is applied to the fluids, such as in a water-injection experiment, the applied forces tend to distort the oil-water interfaces. However, in most fine-grained, water-wet sands, the applied pressure difference across one or two grain diameters is usually several orders of magnitude less than the capillary pressure difference. These con-siderations lead to the theory&apos; that even during flow the capillary forces continue to control the microscopic distribution of oil and water within the pores of a porous material for all practical reservoir and laboratory flow rates. This concept of capillary forces controlling the microscopic distribution of fluids has been substantially verified by other investigators3-7 who have found a lack of dependence of relative permeability and residual oil saturation on rate of fluid injection. Macroscopic Distribution The microscopic influence of capillary forces cannot be observed easily and only the effect on the macroscopic or average saturation can be detected. The saturation, of course, is really the point of interest. During a water flood, large differences in saturation at the flood front cause large capillary pressure gradients. This, in turn, causes water to advance ahead of the flood front thereby reducing the capillary pressure gradient in this region. The result is that in homogeneous porous media capillary pressure gradients tend to cause a diffuse displacement front. At low rates in laboratory columns, the front may extend over the entire column length. When the advancing water first reaches the outflow face of a core, the water, which is the wetting phase, cannot be produced because the pressure in the water just inside the core is lower than the pressure in the oil-filled space around the outflow face. This difference in pressure is equal to the capillary pressure for the water saturation existing at the outflow face. Water, therefore, accumulates at the outflow end of the core which causes a reduction in the capillary pressure. Because the capillary pressure does not vanish except at the residual oil saturation,7,8,9 water will not be produced until the residual oil saturation exists at the outflow face. This entire effect,"&apos; which is called the "boundary effect", results in a region of relatively high water saturation near the outflow face. At low rates of injection in a short column, this region of high water saturation may extend over a considerable portion of the column. The influence of capillary forces on the macroscopic flow of oil and water have been described by Leverett.10 For unidirectional, viscous flow in the absence of gravity segregation, the expression in dimensionless form for the fraction of water in the flowing stream, f, is

Jan 1, 1958

By Sidney Fischler

Large striation-free single crystals of bismuth have been grown from the melt by rapid freezing. Zone-refined bismuth, together with doping impurities if desired, is placed in a shallow flat-bottomed graphite boat and melted in air with a propane hand torch. The torch is then withdrawn in a manner which causes the melt to freeze direction-ally. Crystallization, which resuires only a few minutes, usually results in the formation of a single crystal even when a seed crystal is not used. Crys -tals of any desired orientation may be grown by using oriented seeds. Undoped crystals grown by this method have residual resistivity ratios greater than 200. THE growth of large single crystals of bismuth by either the Czochralski or horizontal zoning technique is not entirely satisfactory. Specifically, difficulties are encountered in producing single crystals of the required dimensions in all desired orientations, and striations caused by low-angle polysynthetic twins are frequently present in the crystals. In addition, both methods are time-consuming and require special apparatus of some complexity. A simpler method has now been developed for growing large striation-free bismuth single crystals of desired orientation in a short time. Fig. 1 shows a typical setup consisting of a rectangular graphite boat which contains zone-refined bismuth, a 1/8-in.-thick flat quartz plate which covers the entire inner bottom of the boat, and three additional quartz plates about 1/4 in. thick which are used to separate the bismuth from the graphite everywhere except at a small area at the left of the boat. The graphite boat is 1 in. high, and its sides and bottom are about 1/8 in. thick. The quartz plates should be smooth and clean. The graphite boat is heated from the right with a propane torch, as shown in Fig. 1, until the bismuth is completely melted. The melt has the shape of a triangle with a narrow neck at the apex farthest from the torch. The melt is frozen direc-tionally by gradually moving the torch toward the right, away from the boat. The bismuth in contact with the graphite, at the left end of the neck, freezes first. The freezing interface then moves down the neck into the main bulk of material, where it develops a convex shape ideal for the continuation of single-crystal growth. The interface continues to move through the melt until the entire bulk is solid. The entire procedure may be completed, in air, in a matter of minutes. The technique described almost always yields a single crystal whose basal plane is nearly perpendi,cular to the bottom of the graphite boat. In earlier experiments, in which the bottom of the melt was in direct contact with the graphite boat, single crystals were grown with basal planes parallel, perpendicular, or at some intermediate angle to the bottom of the boat. At times the orientation of the bulk of the material differed from the orientation of the material in the narrow neck. In these cases, a nucleation site initiated the growth of a differently oriented crystal, and the thermal conditions favored the new orientation over the initial one. The thermal conditions depend on a number of factors, including the heating technique, the placement, shape, and thickness of the quartz plates, the thickness of the walls and bottom of the graphite boat, and the quantity of bulk bismuth employed. All of these factors, plus the initial orientation and the presence and effectiveness of nucleation sites, will determine the orientation of the final large single-crystal slab. When a crystal of specific orientation is desired, an oriented section of a rapid-freeze crystal is shaped by spark cutting and grinding for use as a seed. To grow a doped crystal, the desired impurity is placed in the graphite boat together with the bismuth chunks and seed. Crystals doped with mercury, cadmium, lead, and selenium have been grown. The rate of freezing is so great that the distribution coefficient of any impurity approximates unity. On a gross scale, therefore, impurities should be more homogeneously distributed in rapid-freeze crystals than in Czochralski or zoned crystals. Because of the possibility of constitutional supercooling, however, it is quite possible that impurities are not homogeneously distributed on a microscopic scale in the rapid-freeze crystals. Generally the single crystal slabs which have been prepared are initially 5 to 7 mm thick. Thicker crystals may be obtained by using one of these slabs as a seed. The slab is placed in a graphite boat resting on a large aluminum block, either air- or

Jan 1, 1964

By R. Wild, F. A. Wright

When a blast furnace has a certain defined burden and is operated under fixed conditions of blast temperature, etc., the fuel efficiency is determined by the extent to which the reducing gases can remove oxygen from the burden in the furnace stack. This is determined by two distinct factors: 1) The uniformity of gas-solid contact, and 2) The ease with which oxygen can be removed from individual pieces of burden. This latter is often called burden reducibility. When burdens were poorly prepared the first factor was by far the most important and a study of the reducibility of individual lumps was of rather academic interest. In recent years good burden preparation with emphasis on uniformly sized material has led to greatly improved gas distribution in the stack, and thus the second factor has become much more important and there has been a marked increase in interest in methods of measuring reducibility. This paper explores the Linder method of measuring such reducibility. The measurement of reducibility of burden materials must be carried out under conditions duplicating, as nearly as possible, those of the blast furnace stack. This is very difficult since the blast furnace process is a counter-current one, and thus the initial conditions encountered by the solid (gas temperature, composition, etc.) are the result of heat and mass transfer occurring lower down the stack. Any method of burden testing which does not take this into account is, at least to some extent, based on arbitrary assumptions. In an attempt to study blast furnace reactions under non-arbitrary conditions BISRA adopted the SCICE technique as a method of investigation. This technique has been used with a measure of success.&apos; The SCICE technique, however, was found to be too slow for use as a routine test for burden materials and it was decided to construct additional equipment for burden testing. A test was required which would: 1) Be as realistic as possible. 2) Be quick and easy to operate. 3) Give some indication of the breakdown likely to take place during reduction in addition to a reducibility index. After a critical assessment of the reducibility tests which have been proposed it was decided to adopt the Linder test equipment and procedure as a basis for burden testing. THE LINDER TEST APPARATUS AND PROCEDURE The apparatus which was constructed (Fig. 1) was the same as that described by Linder2 except for minor changes in design. Linder also laid down a test procedure which he had derived from the results of investigations on Swedish blast furnaces. The variations of temperature and gas composition during the test were defined; these are shown diagram-matically in Fig. 2. BISRA&apos;s intention was to use the standard temperature and gas composition programmes for testing a variety of burden materials and also to investigate the influence of different programmes on standard burden materials, making use of information from the SCICE apparatus wherever this is possible. Up to the present, effort has been concentrated on the first part of the programme, and work on the second part has only just commenced. For each test 200 g of coke and 500 g of burden material were used. Linder had recommended that the coke and burden material should be between 1 and 1 1/2 in. and this was adhered to in early experiments on ores and sinters. Since the eventual aim of this work was to relate the test results to blast furnace operation, it was decided to carry out subsequent experiments using burden material in the size range used in the blast furnace, as far as this was possible. If the main interest was, for example, a comparison of the products resulting from different methods of agglomeration, then there would be advantages in using burden materials as close as possible to a standard size. After the charge had been placed in the reaction tube and this had been connected to the gas supply, rotation of the reaction tube at 30 rpm was started and the reduction programme was commenced, the gas temperature and composition being manually controlled according to the programme shown in Fig. 2. After the reduction test the charge was cooled in a nitrogen atmosphere. It was then removed from the reaction tube, the coke and burden separated, and the extent of burden breakdown assessed by screening it at 10 and 30 mesh. The extent of reduction was then

Jan 1, 1964

By O. G. Paasche, Yuan-Shou Shen

THERE is a disagreement among the various authors about the exact manner of transformation of ZrCr2. Rostokerl and others2 stated that ZrCr2 had a C-14 (MgZn2) type of structure below 1000°C and a C-15 (MgCu2) type of structure at temperatures above 1000°C. Alisova3 and others4 reached the opposite conclusion and stated that the transformation temperature is close to the melting point of ZrCr2. A literature survey shows that various investigators3&apos;= who homogenized the specimens at a temperature higher than 1000°C have concluded that ZrCr2 had the C-15 structure at room temperature. Meanwhile, Jordan et al.4 reached similar conclusions without annealing the specimen. Other investigators1,2,6,7 who X-rayed the specimens in the as-cast condition without annealing reached different conclusions. The investigation reported herein was conducted with the aim of exploring the exact manner of transformation of ZrCr2 by various heat treatment tests. The alloys for this examination were prepared from iodide-reduced zirconium crystal bars, 99.9 pct purity, and electrolytic chromium, 99.9 pct purity. They were melted in a nonconsumable electrode arc furnace with water-cooled copper crucible in a helium atmosphere. The melting loss of each alloy was less than 1.5 pct by weight. Chemical analysis of a randomly selected specimen indicated that there was a very close agreement between calculated and analyzed compositions. Before being heat-treated each specimen was encapsulated in a vycor or quartz tube inside which an argon atmosphere was maintained at a pressure of lower than 1 atm. In determining the crystal structure of each specimen with a Debye-Scherrer camera, the standard procedure8 for X-ray quality analysis (Hanawalt method) was followed. The different series of heat treatment tests in this investigation are tabulated in Tables I and 11. The tests in Series I, specimens from 1-1 to 1-9, which were similar to Rostoker&apos;s experiment1 indicated that the transformation temperature seemed to fall between 870° and 900°C and that the crystal structure of ZrCr2 at lower temperature seemed to be of the C-14 type. However, once the compound is transformed to C-15 type, it is impossible to reverse the transformation back to the C-14 type by first heating the specimen above 900°C and then annealing it slowly below 900°C as shown in Experiments II-1 to II-3. Thus, it appears that the specimen of ZrCr2 will transform from C-14 to C-15 structure when heated above 900°C but will not transform from C-15 to C-14 when annealed slowly passing 900° C even after the extremely slow cooling process such as indicated in the experiment of Specimen II-3. As a valid transformation temperature is a temperature at which the transformation is reversible, therefore the temperature 900°C (or other temperature close to 900°C) is not the transformation temperature for ZrCr2 and the C-14 structure is not the stable structure of ZrCr2 at lower temperatures. The C-14 structure is retained at room temperature because the transformation to C-15 structure is very sluggish and the fast cooling after melting does not allow enough time for the transformation to take place. Additional energy is required to alter the metastable condition of the C-14 structure. The sluggishness of this transformation was again demonstrated through another series of experiments. Four specimens with C-14 structure were taken. Then they were annealed at 900°C but each specimen was soaked for a different period of time, Table 11. X-ray diffraction patterns of this group indicated that the C-14 structure gradually disappeared as the soaking period was lengthened. The figures listed under the column "C-14 Structure, pct" were estimated from the intensity of the d = 2.330 line of the diffraction pattern corresponding to the structure. Notice that the intensity of this line became weaker for longer soaking periods. To determine the transformation temperature of ZrCr2, specimens with C-14 structure (as-cast condition) were annealed at 1300°, 1400°, 1500°, 1550°, and 1600°C, respectively. A final specimen was first heat-treated to 1500°C in order to transform it to C-15 structure, then heat-treated at 1600°C again. From the X-ray analyses of this series of tests, Specimen Nos. III-1 to III-6, it is evident that a transition from C-15 structure at lower temperatures to the C-14 structure occurs at some temperature between 1550° and 1600°C.

Jan 1, 1969

By L. C. Chang, T. A. Read

Diffusionless transformation in Au-Cd single crystals containing about 50 atomic pet Cd was investigated by means of X-ray analysis of the orientation relationships, electrical resistivity measurements, and motion picture studies of the movement of boundaries between the new and old phases during transformation. The nucleation of diffusionless transformation by imperfections and the generation of imperfections by diffusionless transformation were discussed. THAT connections exist between plastic deformation and diffusionless phase changes has long been recognized. Thus it is often possible to produce a diffusionless phase change in a temperature range, above that in which the change occurs spontaneously, by cold-working the initial phase. Certain aspects of the dislocation theory of the plastic deformation of crystalline solids also provide for a rather direct connection between the processes involved in plastic deformation and in diffusionless phase changes. Heidenreich and Shockleyl have pointed out that simple edge dislocations in f.c.c. metals are probably unstable, and that the more probable lattice imperfections, called extended edge dislocations, consist of two half dislocations separated by a distance of the order of magnitude of 100A. The region about two atomic planes thick between the half dislocations because of this stacking fault may be described as having the hexagonal close-packed structure. Presumably the stacking faults observed by Barrett" fter cold-working f.c.c. Cu-Si alloys resulted from the passage of such half dislocations through the lattice of the initial phase. It is now becoming clear that the development of a detailed theory of the atomic movements involved in diffusionless phase changes will require a consideration of the role played by lattice imperfections, just as such considerations are necessary to the understanding of plastic deformation mechanisms. This point of view has been recently set forth, for example, by Cohen, Machlin, and Paranjpe3 who pointed out the role which might be played by screw dislocations in nucleating diffusionless phase changes. The present paper reports on some aspects of the diffusionless phase change in single crystals of the beta phase alloy Au-Cd which serve to emphasize further the importance of lattice imperfections in diffusionless phase changes. The diffusionless phase change of Au-Cd possesses several remarkable features. One of these is that the interface between the high-temperature beta phase and the low-temperature orthorhombic phase typically moves with a low velocity, in contrast to the behavior observed in the transformation of austenite to martensite. Motion pictures of this slow interface motion have been prepared in the course of the work reported here. Another important feature of the Au-Cd transformation is the small amount of undercooling observed. The reverse transformation occurs on reheating to a temperature only 20" higher than the transformation temperature observed on cooling, and under some circumstances the hysteresis observed is substantially less than this. This narrow temperature range between transformation on heating and cooling is presumably in part a consequence of the fact that the transformation requires a lattice shear of only about 3". Finally, the orthorhombic product phase possesses unusual mechanical properties, as was first pointed out by olander&apos; and Benedicks." After completion of the transformation on cooling the specimen can be severely deformed, yet on the release of load it springs back to its original shape in a rubber-like manner. Explanation of this phenomenon will require an understanding of the lattice imperfections in the orthorhombic structure and, correspondingly, of those in the initial body-centered cubic structure. Single crystals of Au-Cd alloy containing 47.5 and 49.0 atomic pct Cd were prepared from fine gold (99.95 pct purity) and chemically pure cadmium (99.99 pct purity) by melting the alloy in an evacuated and sealed fused quartz tubing and growing into single-crystal form by the Bridgman method. The Au-Cd alloy containing 47.5 atomic pct Cd undergoes a diffusionless transformation from an ordered body-centered cubic structure to an orthorhombic structure when it is cooled to about 60°C, while the reverse transformation takes place when the alloy is heated to about 80°C, according to electrical resistivity studies. The structures of these two phases have been studied by Blander,4 reinvestigated by Bystrom and Almin.e he lines of Debye photo-gram of powdered samples of Au-Cd alloy containing 47.5 atomic pct Cd prepared in this laboratory were identified and agreed fairly well with those of

Jan 1, 1952

By J. H. Swisher

When an Fe-Mn alloy is internally oxidized, the inclusions formed are MnO which contains some dissolzled FeO. In the internal oxidation reaction, not all of the manganese is oxidized; some remains in solid solution as a result of the high Mn-0 solubility product in iron. Taking these factors into consideration, the rate of internal oxidation of an Fe-1.0 pct Mn alloy is computed as a function of temperature, using available thermodynanzic data and recently published data for the solubility and diffusivity of oxygen in iron. The predicted and experimentally determined rates for the temperature range from 950 to 1350°C are in good agreement. ThE rates of internal oxidation of austenitic Fe-A1 and Fe-Si alloys have been studied extensively.1"4 Schenck et al. report the results of a few experiments with Fe-Mn alloys at 854" and 956C, and Bradford5 has studied the rate of internal oxidation of commercial alloys containing manganese in the temperature range from 677" to 899°C. When Fe-Mn alloys are internally oxidized, the inclusions formed are solutions of FeO in MnO, the composition depending on the experimental conditions. Since the thermodynamics of the Fe-Mn and FeO-MnO systems have been investigated,6"9 and since the solubility and diffusion coefficient of oxygen in y iron have been determined recently,&apos; it is possible to predict the rate of internal oxidation from known data. The calculations used in predicting the rate of internal oxidation will first be outlined, then the results of the prediction will be compared with the experimental results of this investigation. PREDICTION OF PERMEABILITY FROM THERMODYNAMIC AND DIFFUSIVITY DATA Oxygen is provided for internal oxidation in these experiments by the dissociation of water vapor on the surface of the alloy. The dissociation reaction is: + H2(g) + [O] [1] where [0] denotes oxygen in solution. The equilibrium constant for this reaction is known as a function of temperature:&apos; log As oxygen diffuses into the alloy, oxide inclusions are formed which are MnO with some FeO in solid solution. The reactions occurring are: [Mn] + [0] = (MnO) [31 and [Fe] + [0] = (FeO) [41 where [ Mn] is manganese dissolved in iron and (FeO) is iron oxide dissolved in MnO. The overall reactions may be written as follows: [Mn] + HOte) = (MnO) + H2(£) [5] and [Fe] + H20(g) = (FeO) + Hz(R) [61 The standard free-energy changes and equilibrium constants for Reactions [5] and [6] are known.6 Therefore the equilibrium constants for Reactions [3] and [4] may be obtained by combining known thermodynamic data for Reactions [I], [5], and [6]. For Reactions [3] and [4]: K = and For the present purpose, both the Fe-Mn7,8 and FeO-~n0&apos; systems can be considered to be ideal, i.e., [amn] = [NM~] and (aFeO) = (NM~~) = 1 - (NFeO) where the Ns are mole fractions. These relations, together with Eqs. [I] and [8], permit us to compute both the oxide and metal compositions as a function of temperature and oxygen potential at any point in the specimen. For cases where the oxygen concentration gradient between the surface and the subscale-base metal interface is linear, the kinetics of internal oxidation is an application of Fick&apos;s first law: where dn/dt is the instantaneous flux of oxygen into the specimen, g-atom per sq cm sec; 6 is the instantaneous thickness of the subscale, cm; Do is the diffusion coefficient of oxygen in iron, sq cm per sec; p is density of iron, g per cu cm; h[%O] is the oxygen concentration difference between the surface and sub-scale-base metal interface, wt pct. B6hm and ~ahlweit" derived an exact solution to the diffusion equation for systems in which there is a stoichiometric oxide formed. They showed that the oxygen concentration gradient is given by a rather complex error function relation. For the Fe-Mn-0 system and for most other systems that have been studied, however, variations in oxide compositions are small and rates of internal oxidation are sufficiently slow that the deviation from linearity in the concentration gradient of oxygen is negligible. The mass of oxygen transported across a unit area of the specimen for the total time of the experiment is given by the mass balance equation:

Jan 1, 1969

By W. B. Gogarty

The reported decreases in water mobility do not seem unusual in view of non-Newtonian fluid properties. Shear stress vs shear rate diagrams have been reported for other solutions of water-soluble polymers. Some of these polymers are similar to the type mentioned by the author. Generally, the shear stress-shear rate is a non-linear function for these solutions. Data for plotting apparent viscosity vs shear rate can be obtained from this function. Apparent viscosity is defined as the ratio of shear stress to shear rate at a given shear rate. When plotted, the apparent viscosity decreases with increasing shear rate. This behavior is typical of a pseudoplastic fluid. For some water-soluble polymer solutions, the apparent viscosity decreases more than 50 times while the shear rate increases 1,000 times. Thus, viscosity of a pseudoplastic fluid only has meaning at a specified shear rate. Results of Fig. 1 could be explained in these terms. Viscosities measured in the Ostwald viscometer represent values at a given shear rate. Some average shear rate is affecting the polymer solutions while flowing through the core. This average value fixes the apparent viscosity as long as the flow rate remains constant. Viscosities measured by the two methods will be equal if shear rates are the same. The results indicate that shear rate in the core is lower (higher apparent viscosity) than in the viscometer. In the paper by Johnson, Bossler and Naumann, the relative permeability is independent of viscosity ratio. Thus, the relative permeability with respect to water flow at residual oil should be independent of the flowing phase viscosity. Polymer solutions will appear as Newtonian fluids The discussion emphasizes the nature of the "resistance factor effect" as discussed in the paper. Repeated anomalies arising in hundreds of experiments led us to the conclusion that non-Newtonian flow is not the only factor. Several of the key anomalies are as follows: 1. Measured viscosities over a range of shear rates from <1 sec-&apos; to 1,000 sec-&apos; do not account for but a minor fraction of the R observed in cores when compared in similar shear-rate ranges. 2. The slope of R vs flow rates in cores is always different from that expected from viscometer shear-rate measurements as shown in Fig. 2. in a core, the level of viscosity being fixed at a given flow rate. With these conditions, the definition of resistance factor R by Eq. 2 is simplified to Since , is constant with rate, R becomes a measure of the apparent viscosity in a core at a given flow rate. Variation in flow rate could easily account for the changes of R shown in Fig. 5. Also, this points to the fallacy of assuming R to be a unique parameter. The constant resistance factors at different flooding velocities appear to be in disagreement with the above discussion. The author furnishes Fig. 2 to support his arguments. As shown, the resistance factors remained substantially constant in the two cores over a considerable range of flooding velocities. However, in the 73-md core, the factor increases at lower rates. This behavior agrees with known characteristics of some pseudoplastic material. These materials act both as Newtonian and as non-Newtonian fluids in different regions of shear rate. Some exhibit first Newtonian, then non-Newtonian, finally, Newtonian character. Others are first non-Newtonian and then Newtonian. This latter type would explain the results with the 73-md core. The Fann-instrument results are not significant since shear rates in the core may be much different than with the viscometer. The higher resistance factor at high rates in the 150-md core is more difficult to explain. The greater resistance at increased flow rates could be attributed to what might be termed temporary bridging. As envisioned, changes in polymer configuration occur at the higher energy associated with the increased flow rate. These changes could cause less effective passage of polymer through the core. Correspondingly, increases in pressure drop will occur. These will be interpreted as higher resistance factors. 3. Most polymer solutions are non-Newtonian and many are more shear-rate sensitive than the polymers in question, yet only a very few polymers demonstrate useful R values. Gogarty&apos;s assumption that viscosities in cores and vis-cometers will be the same if measured at the same shear rate is only valid if non-Newtonian rheology is the only parameter. The experimental evidence does not validate this assumption. The anomalies observed in the equilibrium displacement experiment shown in Fig. 5 are not explained on the basis of varying flow rates since the rates were held constant. M

Jan 1, 1965

By Dennis E. Stover

Grade control for in situ uranium leaching is maintaining, at desired levels, the uranium concentration in the pregnant lixiviant which feeds the extraction (ion exchange) circuit. This differs from grade control in conventional mining in that in situ grade control is imposed subsequent to rather than prior to leaching without the direct observation and control possible in conventional mining and milling. Grade control is a necessary engineering task through the entire project life, beginning with preliminary evaluation and design and ending only when the final wells are shut in. More specifically, this task is associated with designing the initial well field, maintaining productivity during well field operations, and planning well field expansions to compensate for the depletion of existing wells. Our aim during each of these phases is to maximize uranium productivity while ensuring that we are developing information necessary for future phases. Throughout this task, we remain cognizant of the fact that uranium productivity is a function of both the complex geologic and operational parameters of the project. A minimum list of significant geological factors must include the following: . Host formation mineralogy . Uranium mineralogy . Permeability . Ore quality (grade and thickness) Our concerns are not limited to average or general descriptions of these factors. The interactions among the factors as well as localized variations among them are far more important in obtaining high productivity from a deposit. For example, an ore body may display an average permeability of one darcy but have its high grade ore confined to regions with permeabilities less than 500 millidarcies. This relationship between ore grade and permeability must be understood early in the project life if the operation is to be successful. Similarly, the fundamental operating parameters for the well field include those items which enable us to distribute the lixiviant within the ore as well as the chemistry which will dissolve the uranium minerals. A minimum list of such factors will include: . Well design . Well efficiency . Well bore damage . Pattern size and shape . Oxidant type and concentration . Complexing agent concentration - pH The interactions between these variables and the complex geological variations create a situation which often defies quantitative analysis. Hence, we have adopted a statistical approach when correlating production history with these parameters and the quality of the correlations improves as the number of wells operated increases. However, the correlations are often specific to an ore body. We find that we must tailor the process to meet the unique geologic parameters of each ore body. PHASE 1: INITIAL WELL FIELD DESIGN Designing the initial well field is perhaps the most difficult phase because we have the smallest data base from which to predict performance. We will have conducted numerous laboratory tests and, perhaps, field pilot tests to select the lixiviant system and to characterize the geologic parameters. However, we will learn a great deal more about the deposit and its productivity during actual commercial scale operation. Fully acknowledging its limitations, we will, as a starting point, assume that uranium productivity will be directly proportional to the quality and quantity of recoverable reserves. Future deviations from this assumption will be plentiful and result from our limited understanding of the aforementioned interactions between and among the operational and geological factors. However, in planning the initial field, estimation of the quantity of leachable uranium present at levels above the economic grade and grade-thickness limitations is a priority task. (The concentration of uranium in the ore, the ore grade, is expressed in units of weight percent. The grade-thickness of the ore is the product of the average grade and ore thickness expressed in units of percent-feet.) These parameters provide a direct indication of the quality and quantity of ore. They are determined from gamma logging of closely spaced drill holes (50 to 100 foot centers being typical) accompanied by uranium core analysis or direct uranium assay logging. Gamma- logging measures gross gamma radiation which emanates from uranium decay products and indicates only the possible presence of uranium. Direct uranium assays are necessary to confirm this presence and the true location and quality of the reserve. From this information, an estimate of the in-place uranium reserve is formulated. Utilizing the above data, we begin to assess the quantity and quality of the leachable reserve. Analysis of self-potential and resistivity logs in conjunction with uranium logs will identify those zones which contain uranium and display apparent high permeabilities. Similarly, zones with extensive calcite cementation or dense clay sedimentation are located and uranium within such zones is excluded. (Interpretation of these logs should be confirmed

Jan 1, 1980