Search Documents

By E. C. Hopkinson, A. H. Youmans, R. A. Bergan, H. I. Oshry

A new log has been developed for quantitative formation evaluation which is based on a measurement of the length of time slow neutrons survive before they are captured in the rocks and fluids. The logging instrument employs a cyclically pulsed neutron generator and a gated scintillation counter which is synchronized with the source. The source emits short, intense bursts of 14 mev neutrons once every 1,000 microsec and is quiescent between bursts. During the period the source is quiescent, the detector is electronically actuated for two independent preselected intervals. A comparison of the counting rates during these two intervals gives a measure of the rate of decay of the slow neutrons and of the associated gamma radiation. The average neutron lifetime in most earth formations is in the range from 50 to 500 microsec. It can be measured during a continuous logging operation at conventional logging speeds. The design of the logging instrument is described and the results of tests are compared with theoretical predictiom. Formulas are developed which give the relationship between log response and formation properties. It is shown that the method is particularly sensitive to formation fluid salinity, and that salt water saturation can be measured accurately in either cased or open hole. The measurement can be made independent of borehole size, fluid type, casing and tool position in the hole by properly selecting the intervals during which the measurements are made. The results of tests with a prototype logging tool are given. INTRODUCTION A new nuclear logging system has been developed which employs the Accelatron,* an accelerator-type neutron source, and accurately measures formation brine saturation in an entirely new way. It has produced a type of formation log with better sensitivity, greater sampling depth and simpler quantitative interpretation than any other nuclear log thus far suggested. The new Neutron Lifetime Log* employs a pulsed electromechanical neutron source and a synchronously gated radiation detector. A prototype instrument has been field tested during recent months to demonstrate the operability of the apparatus and the feasibility of the method. Tests in wells and simulated boreholes have confirmed theoretical predictions and have shown that formation param ters can be measured independent of casing and other borehole parameters. Preliminary results of field tests have indicated that the log may have important and widespread applications. BASIC PRINCIPLE OF NEUTRON LIFETIME LOG The Neutron Lifetime Log is based on the fact that neutrons emitted by a source in a well are rapidly but not instantly captured by the material around the source. Their capture is a matter of statistical probability; the greater the number of capturing nuclei and the greater the "capture cross section", the greater is the probability that a neutron will be captured quickly. The average life of a thermal neutron in vacuum is about 13 minutes, but in common earth materials, the average neutron life ranges between extremes of about 5 rnicrosec for rock salt and perhaps 900 microsec for quartzite. The Neutron Lifetime Log responds to variations in this average neutron life. The theoretical basis for a log of this general type has been well understood by nuclear logging experts in many laboratories both in America and in Russia, and develop mental work along these lines has been in progress for many years. The Russian literature has reported both theoretical and experimental work1,2 but in this country there have been no published reports of progress toward a practical logging instrument. The logging instrument is designed to measure radiation produced by slow neutrons during selected intervals when no neutrons are being emitted by the source. The source is arranged to emit neutrons in bursts or pulses. During the quiescent interval between the pulses, it is possible to observe the exponential "decay" of the neutrons and the neutron-induced radiation as the individual neutrons progressively disappear due to capture by atoms in the formation or the borehole. When a short pulse of 14 mev neutrons is emitted by a source in a borehole, the individual neutrons are slowed to thermal energy within a few microsec. Thus, a cloud of "slow" neutrons is formed around the source within 10 to 50 microsec after the pulse. This cloud is most dense within a few inches of the source, and is progressively less dense out to a radius of about 3 ft, where radiation from the source is practically undetectable.

Jan 1, 1965

By Anton Sawatzky, Erich Vogt

By means of mathematical solutions to the appropriate diffusion equations, we describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various temperatures and concentrations encountered in a heavy water moderated reactor. When the hydrogen concentration is below terminal solid solubility only the a Phase is present. Redistributions are then described in terms of the characteristic functions of the difhsion equation. For higher concentrations both the a and 6 phases are present. We assume the two phases to be always in equilibrium. For moderately small hydrogen concentrations exact solutions of the two-phase equation approach the the approximate solutions derived by Sawatzky and for all concentrations the exact solutions exhibit the qualitative features of his result: the two-phase concentration increases with time, everywhere; in the absence of a hydrogen current at the hot end of the sample an a-phase region always exists there; the interface of the a + 6 , a-phase boundary moves toward the cold md of the sample and the hydrogen concentration is discontinuous at the interface. Simultaneous solulions of the a and a + 6 hydrogen distributims and of the concomitant interface motion are obtained and compared to the observations of Sawatzky and Markowitz. The kinetics of the hydrogen diffusion process are shown to lead to m apparent heat of transport of the a phase which is lower than the actual value (even for samples with long anneals) thus resolving at least partially the disparity between experimental measurements of this quantity. A number of recent papers1"4 have reported measurements on the diffusion and redistribution of hydrogen in Zircaloy-2 under temperature and concentration gradients. These studies were instigated by problems arising from increasing use of Zircaloy-2 as a fuel element cladding material in pressurized-water power-reactors. The Zircaloy-2 picks up hydrogen during the operation of the reactor: the consequent precipitation of zirconium hydride in the Zircaloy-2 has pronounced effects on its mechanical properties. The Purpose of the present Paper is to describe the kinetics of the thermal diffusion of hydrogen in Zircaloy-2 for the various hydrogen concentrations and temperatures likely to be encountered in reactors. When the hydrogen in the Zircaloy-2 is entirely in the solid solution phase (a phase), the differential equation for thermal diffusion is well known and the redistribution can be described by standard mathematical methods some of which are given in Section 11 below. The treatment of the a + 6 (hydride) region differs from the earlier treatment of sawatzky3 by taking into account several modifications of the two-phase diffusion equations as suggested to us by Markowitz4 and Kidson.5 Even with the modifications the results obtained in our more complete treatment are substantially the same as those found by Sawatzky. As we show, the difference between the results of sawatzky3 and kIarkowitz4 is largely due to the difference in the geometry of their experiments. In the next section we derive the modified two-phase equation for arbitrary geometry. The exact solution of this equation is given in Section III for linear and cylindrical geometry. It is shown that Sawatzky's approximate solution is quite accurate for almost all the temperatures and hydrogen concentrations which are actually encountered. In Sawatzky's approximate theory the hydrogen concentration everywhere in the two-phase region increases continuously. As his paper pointed out, this result, together with hydrogen conservation, implies that in a sample with no hydrogen current flowing into the hot end a two-phase region is always accompanied by a single-phase region at the hot end of the sample. The net hydrogen gain in the two-phase region is supplied by the decrease of hydrogen in the single-phase region and by the movement of the (a, a + 6) boundary toward the cold end of the sample. Hydrogen conservation at the (a, a + 6) boundary leads to a discontinuity in the concentration and its derivative there. In Section IV it is shown how these qualitative features of the thermal diffusion kinetics arise from the simultaneous solution of the a-phase differential equation and a + 6 phase equation. Methods derived by us previously for the solution of the redistribution in both phases and the accompanying motion of the boundary are used to obtain approximate solutions valid for large times. The solutions account well for the observed redistributions of Sawatzky and Markowitz. It is shown how the continuing motion of the (a, a + 6) boundary leads to measured values of the heat of transport lower than the actual value, even for specimens with relatively long anneals.

Jan 1, 1963

By M. H. Yoo

Possible interactions of the perfect dislocations of six slip systems or the c dislocation with the (10i2f (ioii), {ioIi}(ioiZ), {1122}(1123), and {1121}(ii26) type twins in hcp metals have been analyzed from the crystallographic and the energetic points of view. Twenty-six distinct types of possible interactions were identified, and those selected based on crystallographic constraints were examined for their energetic feasibilities by use of the anisotropic energy factors. No long-range elastic interaction exists for a dislocation when its Burgers vector is parallel to the twin interface. Under a suitable applied stress, a screw dislocation can cross slip at the twin interface. For basal mixed dislocations in cadmium and zinc, the interaction with {1012} twins is found to be attractive, indicating that incorporation of these dislocations into the twins is energetically feasible and that twin growth will result. On the other hand, the interaction between both basal and Prism mixed dislocations and the {1012} and (1121) twins is found to be repulsive in Mg, Co, Re, Zr, Ti, Hf, and Be. This indicates that under an applied stress a local stress concentration will develop due to a dislocation pileup at the interface, which may result in a site for either the nucleation of other twins or the formation of a crack, depending on the cleavage strength. WHEN a metal undergoes plastic deformation, a certain configuration of slip dislocations will result in a state of dislocation pileup against an obstacle. The stress concentration thus developed may enhance the process of twin nucleation and also twin growth. Furthermore, once formed and dispersed in the crystal, twins can act as effective barriers against slip dislocations. The degree of such mutual influence or interrelation between slip and twinning is generally known to be pronounced in the case of hcp, metals. It is also known that deformation by twinning occurs more commonly in hexagonal metals than in cubic metals. In fact, under suitable stress states, all hexagonal metals exhibit {1012) <1011> type twinning.&apos; In addition to this common type, deformation by (1151) <1126> type twinning occurs in zirconium, titanium, and rhenium, which show remarkable ductility.&apos; The importance of twinning during general deformation to the ductility of hcp polycrystals has been briefly discussed in recent review works.2&apos;3 The purpose of this paper is to analyze the interaction between slip dislocations and twins in the hcp structure and to discuss the nucleation and growth processes of twinning and the role of twinning in the <"°" noil) o, 1/3[112O] (OOO2) 1/3[1123] Fig. l—-Slip systems in hcp structure. ductility of hexagonal metals. The problem will be discussed from the geometric and the energetic points of view in a manner similar to that of the previous work on zinc.4 Since hcp crystals deform by several slip and twin systems, numerous interactions result as possibilities. The Burgers vectors of six slip systems and the c dislocation shown in Fig. 1 and the four twin systems listed in Table I are considered here. A complete tabulation of the possible interactions is followed by discussion of those that are more likely to occur on the basis of crystallographic constraints and energetic considerations. 1) CRYSTALLOGRAPHY OF TWINNING The crystallographic elements, K1, K2, n1, and n2, for the four compound twin systems are now well established.= A unit cell with the base vectors n1, and n2 is shown in Fig. 2 for each twin system. The unit cell before twinning is shown in solid line, and the corresponding unit cell after twinning is shown in dashed line. Also shown in Fig. 2 are the following crystallographic parameters: S is the plane of shear, d the interspacing of the twin habit planes K1,Ø Iis the acute angle between n1, and n 2, e is a numerical factor, and q is the number of K, lattice planes intersected by 17&apos;. These parameters can be expressed in terms of the axial ratio, y = c/a, as listed in Table 11. The macroscopic shear strain of twinning, s, and the magnitude of a "unit twin dis-l~cation,"4 bt, are also expressed in terms of y and given in Table 11. In Table 11, K1 and q1 are given in both Miller-Bravais and Miller indices. In double lattice structures, shuffling of atoms in addition to a homogeneous shear of the lattice is generally required if the original crystal structure is to be restored after twinning. The extent of current understanding on this problem of atom shuffling is per- Table I. Four Twin Systems in Hcp Structure

Jan 1, 1970

By L. W. Bahney

(Cleveland Meeting, October, 1912.) THE photograph, Fig. 1, shows the apparatus a little less than half size, consisting of a filtering-flask fitted with rubber stopper, through which passes a bent glass tube, and an extraction-thimble fitted with rubber stopper through which passes a glass tube of 0.2-5-inch bore. Both tubes are connected by a short piece of rubber tubing. A section of a thimble is shown in the photograph; the tube extends to within in. of the tapered end. The object of using the thimble is to remove the acid from the beaker after all the copper has been precipitated. Time is saved, the copper is not exposed to the acid alone, and there are none of the losses attending ordinary filtration. I have accomplished these results by means of a piece of perforated platinum fastened in the end of a 0.25-in. bore glass tube and a filter-mat of asbestos, but after my supply of proper length fiber became exhausted I could not replenish it even after purchasing 14 lots from four different dealers. The above apparatus may be used to remove at least seven-eighths of a supernatant liquid from a settled precipitate without disturbing the latter. The application of the thimble is best shown by partly out-lining the assay for copper, as follows: Dilute the acid solution of copper and other sulphates to 150 cc. in a 200-cc. Jena beaker, place on a hot plate, add 2 drops of concentrated HC1, then place a strip of aluminum in the beaker (this may be bent or straight, as desired). Connect the apparatus, as shown in Fig. 1, with a filter-pump having a, strong suction. When the copper is precipitated, remove the beaker from tine hot plate and insert the extraction-thimble alongside the strip of aluminum. The acid solution will be drawn through the porous tube. Wish the upper end of the aluminum strip with a jet of hot water, wash down the sides of

Nov 1, 1912

H. W. MussEn, Collingwood, Ontario, Can. (communication to the Secretary*):—Doubtless all engineers who have paid more than a casual visit to Russia have come into contact with that formidable document, the " smieta," or estimate of the Russian manager. It is an institution which seems to be inseparable from Russian mining-methods. As Mr. Shockley points out, the year&apos;s costs a agree very closely" with the figures of the smieta made at the beginning of the year. In cases which have come under my notice, I have been satisfied that there had been a good deal of " rigging" of accounts to this end. The sum spent by the manager was carefully kept down to the total of the estimate, because it was well known that no more money would be forthcoming, and when this is done it is not a difficult matter to see that the right amounts come under the right heads in the final accounts. I do not say that this is always the case, but I have come across notable instances. Looking at it from the Russian owner&apos;s point of view, I think that the balance of the argument is usually in favor of the smieta as limiting " impulsive indiscretion" on the part of managers. The Russian Mining Code of to-day leaves much to be desired, but this is thoroughly appreciated by the official world there, and great changes are spoken of for the future. In many, if not in most, cases the laws are interpreted liberally, and a great deal is left to the discretion of the district mining engineer or inspector, with whom it is necessary to keep in close touch. As Mr. Shockley points out, the officials of a mine, who are always Russians, are held personally responsible for accidents resulting to employees, quite independently of any compensation which may be made to the sufferer. This seems startling enough, but I have always found that a penalty is imposed only

Jan 1, 1909

By Edward Keller

(Canal Zone Meeting, November, 1910.) UNDER the title, Labor-Saving Appliances in the Works-Laboratory, I published a paper1 in which was described how multi-manipulations, in a works-laboratory, and in the furnace-room of an assay-laboratory, can be condensed into single manipulations by applying the proper mechanical devices. For example, I now deposit in, or withdraw from, a muffle a set of 48 cupels as one unit. The front row. (8) of these. are blanks or heaters; the other 40, when they have attained the proper temperature in the muffle, are charged simultaneously with the 40 lead-buttons. Three manipulations here accomplish an operation which by the generally customary method requires 136, and this number is only limited by the size of muffle and cupels. This operation is an enlargement of what I have already described in my former paper, and Fig. I shows the improved implements. In the paper referred to I described a gold-silver bead parting-bath, which is the last of the devices used in regular sequence in practice. This bath was designated as being convenient, but was not a labor-saver properly. Fig. 2 of the present paper shows a new device. Instead of the original tray, there are now sectional holders for the test-tubes, each having a wooden handle on either end, so that the holders may be removed from the boiling bath, and the acid or water poured off from each set of tubes (in this case, 7) without waiting to cool. The tubes, held in place by clutches, as shown in Fig. 3, rest in holes in the base-strip, having a smaller diameter than the tubes. Each holder is stamped at either end with a number, so that the bath becomes further useful by permitting several men to use it at the same time without interference. Apart from the handles, the holders are made of sheet-copper. &apos; Trans., xxxvi., 3 to 18 (1906).

Aug 1, 1910

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

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.&apos;*&apos; Study of the adsorption of sodium from an aqueous solution oftheon quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained."." Three main factors which appeared likely to affect the adsorption of sodium are: l—concentration of sodium in the solution, 2—concentration of onotherof cations in the solution, and 3—anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in thesethe amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxyl-ion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory&apos; except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying." To minimize the laborious preparation of quartz, experiments were made to determine .whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na" activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot 11) and 2000 (lot 111) as determined by the Bloecher method." Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.&apos; It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß+ radiation and a 1.30 mev r radiation. The decay scheme is illustrated in the following equation: ß+ NaR-------&apos;8&apos;77NeZ2 3 years The /3 radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang.R The original active material was 1 ml of solution containing 1 millicurie of Na" as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen." In brief, it included the following steps: 1—Ascertainment of linearity between concentration of Na" and activity measured. 2—Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3—Taking precautions to avoid evaporation of water during centrifuging

Jan 1, 1953

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

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.&apos;*&apos; Study of the adsorption of sodium from an aqueous solution oftheon quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained."." Three main factors which appeared likely to affect the adsorption of sodium are: l—concentration of sodium in the solution, 2—concentration of onotherof cations in the solution, and 3—anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in thesethe amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxyl-ion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory&apos; except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying." To minimize the laborious preparation of quartz, experiments were made to determine .whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na" activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot 11) and 2000 (lot 111) as determined by the Bloecher method." Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.&apos; It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß+ radiation and a 1.30 mev r radiation. The decay scheme is illustrated in the following equation: ß+ NaR-------&apos;8&apos;77NeZ2 3 years The /3 radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang.R The original active material was 1 ml of solution containing 1 millicurie of Na" as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen." In brief, it included the following steps: 1—Ascertainment of linearity between concentration of Na" and activity measured. 2—Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3—Taking precautions to avoid evaporation of water during centrifuging

Jan 1, 1953

By R. M. Brown, W. J. Murphy, B. M. Kapadia

An investigatiott was conducted to study the influence of nitrogen, titanium, and zirconium on the boron llardenabilzty effect in a low-carbon constructiona2 alloy steel. The experimental steels investigated exhibited a significant variation in hardenability, the variation being dependent on the interactions of boron, titanium, and zirconium with the nitrogen. Only the boron not combined with nitrogen was effective in increasing hardenability. Titanium, and with lesser effectiveness zirconium, combined with available nitrogen, thereby protecting the boron. The hardenabil-ity effect mas related to an empirical expression for the "effective" boron content, P, deduced from experimental evidence of these interactions. The hardenabzlity effect reached a maximum at about 0.001 wt pct 0, and decreased somewhat as P increased further. The physical understanding of this relationship is discussed. FOR many years boron has been added to steels to obtain high hardenability. Although a great deal of research has been conducted on boron-treated steels, certain aspects of the boron hardenability effect have not been fully understood. For instance, the magnitude of the hardenability effect has been observed to vary markedly, depending on the steelmaking technique, even when the amount of boron in the steel was essentially constant. Furthermore, the optimum amount of this element to be added has not been definitely established. A better understanding of the boron hardenability effect is essential because too small an addition of boron is likely to be ineffective, while an excessive amount can cause brittleness&apos;&apos; and hot shortness. The findings of earlier investigations have shown that the hardenability effect cannot be consistently related to the amount of boron added or retained in the steel. Grossmann observed that in a 0.60 pct C steel the hardenability increased to a maximum with mold additions up to about 0.0025 pct B and then decreased with larger additions. Other investigators5 likewise reported a maximum in the hardenability at about 0.003 pct B. Crafts and Lamont, however, found that in commercial open-hearth heats of medium-carbon steel the hardenability increased linearly with boron up to 0.001 pct and remained essentially unchanged with larger percentages up to 0.006 pct. Other investigators7,&apos; also observed a rather constant hardenability effect in the range about 0.0005 to 0.0035 pct B. These observations and other evidence suggest that the effectiveness of boron in increasing hardenability probably depends, in addition to the amount, on the form of boron retained in the steel, this form being influenced by the presence of other elements. Both oxygen and nitrogen apparently exert the strongest influence on the hardenability behavior, since, at the temperature of liquid steel, boron readily combines with these elements, thereby losing its effectiveness as most experimental evidence seems to indicate. For consistent recovery of the boron effective in increasing hardenability, it is necessary that the oxygen and nitrogen in the steel be either reduced to extremely small amounts by the steelmaking practice or neutralized by combination with other elements before the addition of boron. The importance of achieving adequate deoxidation prior to the addition of boron in order to realize the full hardenability effect of boron has been sufficiently emphasized by earlier investigators. Digges and Reinhart&apos; and others have investigated the role of nitrogen and have shown that nitrogen also interacts with boron and reduces or nullifies altogether its effect on hardenability. Moreover, their work also demonstrated that the addition of strong nitride formers such as titanium and zirconium reduce the deleterious effect of nitrogen on boron hardenability by combining with nitrogen to form stable nitrides. Another element which has a pronounced influence on the boron hardenability effect is carbon. It has been shown7&apos;10 that the hardenability effect of boron diminishes with increasing carbon content, and becomes almost negligible at the eutectoid composition. This observation is useful in comparing the potential increase in hardenability from boron of steels with different carbon contents, but is not relevant to a study of the effects of normal steelmaking variables. The amounts of oxygen and nitrogen in steel vary with the steel composition and steelmaking practice employed. Most commercia1 low-alloy steels are fully deoxidized by the addition of silicon and aluminum, or other strong deoxidizers, which adequately protect the boron from oxidation. In addition, one or more of the elements such as titanium or zirconium are usually added, either separately or in combination with boron, in the form of complex ferroalloys, to protect boron from combination with nitrogen in the steel. However, the actual amount and type of addition employed for a given processing requirement are usually selected by trial and error, and have a rather limited range of applicability. As a result, substantial variations in the hardenability of boron-treated steels are often observed in practice, particularly when the nitrogen content of the steel is a significant processing variable. These variations might therefore be reasonably attributed to the interactions between boron, nitrogen, and titanium or zirconium present in the

Jan 1, 1969

By A. F. Henderson, C. F. Cornell, A. F. Dunyon, D. A. Dahlstrom

Ossi E. Palasvirta (Development Engineer, Oliver Iron Mining Diu., U. S. Steel Gorp.)—The authors are to be congratulated for their interesting article, which thoroughly illustrates the variables inherent in filtration of taconite concentrate. The work and the conclusions based thereon largely parallel the test work done by the writer at the Pilotac plant" and the experience gained with a commercial size agitating disk filter in the same plant. At Pilotac, however, a thorough study was also made of the effect of depolarizing (demagnetizing) the filter feed, and it is the purpose of this discussion to comment on the merits of depolarization of the magnetite concentrate prior to filtering. The work at Pilotac was done in three phases: 1) preliminary laboratory testing with a circular filter leaf of 0.047 sq ft, followed by 2) plant testing using a 4-ft diam, single-disk agitating filter that was purchased on the basis of the pilot tests on the 4-ft model. In the laboratory tests depolarization was achieved by slowly withdrawing&apos; batches of thickened concentrate from a coil producing an alternating field of about 300 oersteds. In plant tests the standard Pilotac procedure&apos; was employed, wherein the pulp falls freely through the depolarizing coil. The preliminary tests in the laboratory at first seemed to indicate that although depolarization of the filter feed decreases the cake moisture, it also tends to decrease the thickness of the cake, thus decreasing filtering rate. The tests with the 4-ft disk filter soon showed, however, that the compactness of the cake, attained during the form period because of depolarization, permitted a considerable decrease in drying time without any sacrifice in final moisture content. Thus, the filter could be operated at a much higher speed, and the overall capacity was higher than with magnetized feed. Because of the great compactness of the cake there was little shrinkage during the drying period, which prevented cracking and subsequent loss in vacuum. This in turn permitted operation with as thick a feed pulp as the diaphragm pumps could handle, eliminating the necessity of pulp density control. On the basis of these findings, the 6-ft agitating disk filter has been operated at 2 rpm, using feed pulps varying from 65 to 73 pct solids. Initially Saran 601 was used as medium, but it was later replaced with a relatively open, tight-twist nylon cloth. Filtering rates up to 750 lb per ft- er hr can be attained with feeds averaging about 70 pct- 270 mesh, and there is no trouble because of cracking. The cake moistures vary between 8.5 and 9.5 pct. To recapitulate, the merits of depolarizing the filter feed may be summed up as follows: 1) The well dispersed pulp shows less tendency to settle in the filter tank. 2) The homogeneous filter pool results in more even cake formation. 3) Because of absence of flocs, great compactness of cake is attained during the form period. 4) The cake does not tend to crack during the drying period. 5) A drier cake is produced. 6) A shorter drying period is necessary, permitting higher operating speed, which in turn results in increased capacity. 7) Density of the feed pulp can be kept as high as the equipment can handle. This increases capacity, since it is directly proportional to the percentage of solids in the pool. A few tests were also made to study the effect of chemical flocculants on filtration efficiency. Results showed that the effects of chemical and magnetic floc-culation were quite similar. Thus the use of a floccu-lant would impair rather than improve the filtering of magnetite concentrate. A. F. Henderson, C. F. Cornell, A. F. Dunyon and D. A. Dahlstrom (authors&apos; reply)—We want to thank O. E. Palasvirta for his comments, particularly in view of the encouraging results obtained with demagnetized taconite concentrate. In our studies an attempt was made to evaluate the effects of depolarizing the feed to the plant filters by passing the slurry through a coil, similar to the method described by Palasvirta. Unfortunately, in our experiments there were no startling improvements in performance level, neither cake rate increase nor cake moisture reduction. However, when slow filter cycle speeds were employed, the filter cake tended to crack and the vacuum level dropped, resulting in an increase in cake moisture content. When demagnetized feed was used during slow speeds, no cake cracking was evidenced and the vacuum level remained constant. Thus the depolarizing coil was found necessary only in cases of cracking. It should be noted that most of our test work concerned a feed of 85 to 90 pct —335 mesh and about 60 pct by weight solids concentration. This contrasts with 70 pct —270 mesh and 65 to 73 pct by weight solids as noted by Palasvirta. Reviewing both sets of results, it might be concluded that depolarizing may be successfully employed to alleviate cake cracking tendencies and may markedly improve cake rates and moistures on the coarser taconite concentrates. Further investigations may disclose the exact relationship of grind and pulp density to the depolarizing action.

Jan 1, 1959

By A. R. Krause, C. Laird

In order to establish whether or not there is a real temperature effect in fatigue (independent of environment) , poly crystalline copper and Cu- 7.9 A1 alloy have been cycled at 298° and 7° K in vacuo and the fatigue lives compared with those in air and in liquid nitrogen. The lives of both copper and the alloy were found to be highly temperature-dependent in the absence of environment. This result casts serious doubt on the validity of the cell structure hypothesis for stage I crack propagation as presently formulated, because it predicts that there should be no such tempevnture dependence. On the other hand, the plastic blunling process is consistent with the result. Effects of environment aside, the homogenization of slip which accompanies testing at low temperature, and at low strains, seems to be the main cause for increased fatigue life. At high strain amplitudes, the fatigue lives of wavy slip materials, typically copper, are independent of temperature.&apos; It is well-known, however, that low-strain lives greatly as as the temperature of testing is decreased. By contrast, the lives of planar slip materials, such as Cu-7.9 pct A1 alloy, increase to an even greater extent with decreasing temperature throughout both the high and low strain ranges.1&apos;2&apos;5 The mechanism of this temperature effect is associated with the earliest stages of fatigue failure,&apos;" crack nucleation, and stage I growth,"&apos; which is slow propagation along slip bands to the depth of a few grain diameters. Such life behavior has been interpreted on at least two different bases. On the one hand, those interested in the temperature effect at high strain amplitudes1 believe that stage I growth occurs by the plastic blunting process of crack propagation.7&apos;9 They explain the effect in planar slip materials by the homogenization of slip* which accompanies fatigue testing at low temper- atures and serves both to delay crack nucleation and to decrease the rate of stage I propagation. On the other hand, Holt and Backofen,2 who have studied the effect in low strain fatigue, believe that stage I growth can be interpreted by a cell structure hypothesis.10-12 They have challenged2 the conclusion that there is a real temperature effect in this regime of fatigue testing and have interpreted the increased fatigue lives almost entirely in terms of the "environmental-protective&apos;&apos; effect of the liquid nitrogen and helium baths used to obtain low temperatures. This interpretation by Holt and Backofen2 may offer a means of discriminating between these two mechanisms as currently formulated and used to explain stage I growth. On the basis of the plastic blunting process applied to stage I crack propagation,7* the low strain fatigue lives of both wavy and planar slip materials should be increased with decreasing temperature. This follows because both materials show increased slip homogenization in this strain regime."13 Consequently, crack nucleation in intensified bands will be delayed and the linking of such small cracks into larger stage I cracks will be difficult. In addition, the blunting process required to lengthen a stage I crack from the order of 2 to 10 (where the strain concentration of the crack begins to overcome the slip homogenization property of the material) will also be retarded. These delays will give rise to longer lives in both kinds of material. In contrast to the blunting hypothesis, no temperature dependence has been predicted on the basis of the cell structure hypothesis, because it is well-known that materials cycled at low temperature show no differences in type of dislocation structure for a given strain amplitude.18"20 If the lives of wavy and planar slip materials do show a temperature dependence when the environment is eliminated as a variable, then it is questionable whether cell structures per se have a fundamental role in fatigue fracture. Accordingly, specimens of copper and Cu-7.9 wt pct A1 have been cycled at 298° and 77°K in vacuo and the fatigue lives compared with those in air and in liquid nitrogen, in order to establish whether or not there is a real temperature effect in low strain fatigue. Since it is difficult to measure the strains in specimens when cycled in vacuo, S-N curves have been used as the basis of comparison. In studying the influence of temperature on fatigue life in ordinary environment, Holt and Backofen2 used the superior basis of E-N curves. However, they also published S-N curves and thus established the relationship between E-N and S-N curves. This relationship is used to support the S-N comparison reported in the present investigation. EXPERIMENTAL Materials. The copper employed in this investigation was of 99.99 pct purity and the cu-7.9 pct A1 was prepared from metals of the same purity. The stock, of 3 in. initial diam, was reduced in size by rolling

Jan 1, 1969

By R. V. Higgins

This paper presents a computer method to obtain the shape factors and equal cell volumes of the channels for any well spacing pattern from a potentiometric model. By using this program the authors have processed the data for the seven-spot, direct line-drive and the staggered line-drive patterns. The data for the five-spot pattern had been previously processed by a noncomputer method and are included for completeness. The shape factors and volumes for the channels are presented in tables for those who want to use them to process data using their own permeability relationships and viscosities of their reservoir oils. The authors have used the data and sets of representative permeability curves to process sample calculationr of waterflood performances. The comparison of the calculated results shows that the influence of well spacing is small. The permeabilities of the reservoir rock to oil and water had a greater influence on oil recovery for a given pore-volume throughput of water than the well spacing pattern. The more water-wet the reservoir rock, the better the possibility of permeabilities which are conducive to good recovery. The viscosity of the reservoir oil also influences the recovery more than the well spacing pattern. The reduction in the percentage recovery of oil with increase in viscosity of the reservoir oils is small when oil viscosities are in the range of 0.1 to 3. Above this range the reductions in recoveries are extensive. Sample comparisons of the time required for different patterns to recover the oil are presented. Results of an example calculation are given to show the effect of the permeability profile on recovery. INTRODUCTION The effect of well spacing pattern on the recovery of oil when flooding with either gas or water has been studied by many investigators. Muskat et al.1 presented an analysis using conductivity, sweep efficiency and unit mobility to the time of breakthrough. Dyes et al.2 used experimental techniques (X-ray shadowgraphs) and different mobility ratios. They presented quantitatively the relationship between mobility and sweep efficiency at and after breakthrough. Hauber3 presented a method to predict waterflood performance for arbitrary well spacing patterns and mobility ratios. Craig et al.,4 using techniques similar to Dyes et al. to determine sweep efficiency for a five-spot pattern, added the use of relative permeability curves at breakthrough and thereafter. Douglas et al.5 sed rela- tive permeabilities and continuously changing saturations throughout the entire five-spot flood pattern. In obtaining their solutions they used finite-difierence equations. Hig-gins and Leighton6,7 also used relative permeabilities and continuously changing saturations throughout the pattern before and after breakthrough. They employed techniques that process a flood-pattern calculation on the computer in about one minute. The methods of Douglas et al. and Higgins and Leighton both checked closely the laboratory results for a wide range of mobility ratios. This paper presents some sample performances calculated by the Higgins and Leighton method that show the effect on recovery of different permeabilities and viscosities using the seven-spot, the line-drive and the staggered line-drive, as well as the fivespot flood pattern. No previous paper has presented these data using different permeability curves and continuously changing saturations throughout the flood patterns. The paper also presents (1) the results and analyses of the flood-pattern prediction, (2) the computer techniques for determining the shape factors and volumes from the potentiometric models for the foregoing flood patterns, and (3) the shape factors and volumes of the channels of the flood pattern in the event reservoir engineers may like to process waterflood calculations using their own permeability curves and reservoir oils. DESCRIPTION OF METHOD VOLUMES AND SHAPE FACTORS The use of channels taken from a potentiometric model (see Fig. 1) to aid in calculating the performances of water floods of nonlinear patterns has been thoroughly explained in the literature.0,7 Therefore, very little theory, discussion, or proof regarding this phase will be repeated in this paper. The computer method presented in this paper to calculate the volumes and the shape factors of the channels of potentiometric models employs the trapezoidal rule for the volumes and the Pythagorean theorem (the hypotenuse equals the square root of the sum of the squares of the two sides of a right triangle) for the shape factors. In calculating the volume of a channel, the area of each cell in the channel is determined and then multiplied by the thickness to obtain the volume. In determining the areas of the cells, trapezoids are constructed whose vertical sides are spaced Ax apart, as shown in Fig. 2. The length of the sides is the difference between an ordinate cut off by the top and bottom of the cell — usually equipo-tentials. The coordinates of the points along an equipo-tential or streamline are obtained by Lagrange&apos;s8 equation of interpolation for which the constants are coordinate points at the intersections. Three intersections for con-

Jan 1, 1965

By M. T. Simnad, G. Derge, I. George

Measurements of current efficiency on iron-silicate slags in iron crucibles showed that conduction is about 10 pct ionic in slags with less than 10 pct silica and about 90 pct ionic in slags with more than 34 pct silica, increasing linearly in the intermediate range. The balance of the conduction is electronic in character. Silicate ions are discharged at the anode with the evolution of gaseous oxygen. Transport experiments show that the ionic current is carried almost entirely by ferrous ions, which may be assigned a transport number of one. THERE has been increased evidence in recent years that the constitution of liquid-oxide systems (slags) is ionic.1-3 The principal studies designed to establish the structure of liquid slags have been by electrochemical methods&apos;, " and conductivity measurements1,6,7 which also have indicated the presence of semiconduction in several silicate systems1,4-0 and in pure iron oxide.&apos; It is well known that many slag-forming metallic oxides have an ionic lattice type in the solid state, and their properties are determined to a large extent by the lattice defects and ion sizes. As Richardson8 as pointed out, the detailed models of liquid slags cannot be found on thermodynamic data only but "must rest on a proper foundation of compatible structural and thermodynamic knowledge, combined by statistical mechanics." A careful thermodynamic study of the iron-silicate slags has been carried out by Schuhmann with Ensio9 and with Michal.10 They obtained experimental data relating equilibrium CO2: CO ratios to slag composition and made thermodynamic calculations of the activities of FeO and SiO, and of the partial molal heats of solution of FeO and SiO2 in the slags. It was found that the activity-composition relationships deviate considerably from those to be expected from an ideal binary solution of FeO and SiO2. However, the partial molal heat of solution of FeO into the slags was estimated to be zero. Their experimental results were correlated with the constitution diagram for FeO-SiO2 of Bowen and Schairer,11 with the results of Darken and Gurry" on the Fe-O system, and with the work of Darken"&apos; on the Fe-Si-O system. All these studies were found to be consistent with one another. The variation of the mechanism of conduction with composition in the liquid iron-oxide-silica system in the range from pure iron oxide to silica saturation (42 pct SiO2) in iron crucibles was reported in a preliminary note." The current efficiency, or conformance to Faraday&apos;s law, showed some ionic conductance at all compositions, the proportion increasing with the concentration of silica. The current-efficiency experiments since have been extended. Furthermore, transport-number measurements have been completed in silica-saturated iron silicates to determine the nature of the conducting ions. Experimental Current Efficiency in Liquid Iron Oxide and Iron Silicates using Iron Anodes: This study was carried out by passing direct current through slags in the range from pure iron oxide to iron oxide saturated with silica (42 pct silica), using pure iron rods as anodes and the iron container as the cathode. A copper coulometer was included in the circuit to indicate the quantity of current passed during electrolysis. Assuming that the cation involved is Fe-+, the theoretical quantity of iron lost from the anode according to Faraday&apos;s law may be calculated and when compared with the actual loss observed, gives an indication of the extent to which Faraday&apos;s law has been obeyed. It also gives an indication of the presence and extent of ionic conduction in the melt. Preparation of the Slags: About 100 g of chemically pure Fe,O, powder is placed in an iron pot which is heated by induction until the contents liquefy. In this way, FeO is produced according to the reaction Fe2O3 + Fe = 3 FeO. More Fe2O3 or SiO, powder is added and, when a sufficient quantity of molten slag is obtained, the induction unit is turned off, the pot withdrawn, and the molten slag poured on to an iron plate. Homogenization and Electrolysis of the Slag: Apparatus—After considerable development, the setup illustrated in Fig. 1 proved to be quite satisfactory. A is an Armco iron cylinder, 1 in. ID and 1/8 in. wall, consisting of three sections placed one on top of the other. The bottom section is a pot about 5 in. long with a small hole drilled in its bottom to allow withdrawal of gases during evacuation of the apparatus. The middle section is 6 in. long and consists of a pot which serves as the slag container, while the top section is a hollow-cylinder continuation of the slag-container pot. The height of this latter section is about 5 in., giving an overall length of approximately 16 in. The iron cylinder is constructed in this way for ease of fabrication, the individual sections becoming welded together after the

Jan 1, 1955

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.&apos; udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4&apos;5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A&apos;-B&apos; develops at the other intersection. The angles A + B and A&apos; + B&apos; are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By Benny Langston, Frank M. Stephens

Although little information is available concerning small-scale equipment for dust collection in laboratories, it is possible to adapt standard equipment for laboratory use. Dust from laboratory processes may be collected by cyclone separators, filters, electrostatic separators, scrubbers, and settling chambers. IN recent years much attention has been given to recovery, treatment, and disposal of dusts discharged into the atmosphere from operations of industry. considerable data has been accumulated on both operation and design of dust-collector equipment for commercial installations. On the other hand, there is almost no published data on design and construction of small-scale equipment to handle dust problems that arise in the ore-dressing laboratory. Dust-collection equipment such as multiclones, single-cyclones, scrubbers, chemical and mechanical filters, settling chambers, and electrostatic separators has proved its efficiency for collecting dust in industry. In the laboratory, however, the engineer is faced with the problem of collecting small quantities of dust, inexpensively, without diverting the major effort from the metallurgical problem to the problem of collecting dust produced by the process. For most applications standard dust-collection equipment is too large for use in the laboratory; however, for control of dust in large working areas it is often possible to use a standard dust collector, such as an air filter, with branch ducts to eliminate a health hazard. For example, the well-furnished sample-preparation room containing small jaw crushers, rolls, and pulverizers, in addition to the riffles and screens necessary for preparation of samples, presents a perennial source of dust. The authors&apos; experience has shown that a combination system consisting of overhead branch ducts to the individual equipment and floor ducts with grills, where applicable, connected to a central dust collector effectively removes dust generated in preparation of samples. Fig. 1 is a sketch of a downdraft dust-collector for table installation. Similar systems can be built with floor grids. For portable equipment such as laboratory vibrating screens this type of installation with a steel grill to support the heavy load is reasonably efficient. Overhead branch ducts to individual crushing and grinding equipment, although efficient, must be carefully controlled by dampers to prevent excess loss or a change in the composition of the sample. Change in sample composition can result from excess velocity, which causes selective removal of constituents of low specific gravity. Fig. 2&apos; shows the theoretical effect of terminal velocity on spherical particles of different specific gravities in air and water under action of gravity. Fig. 3 shows the effect of air velocity on composition of CaCO, coal mixtures. Although the entrainment of dust particles in a moving air stream is the basic mechanism by which all dust-collection equipment functions, usually intake velocity of the dust-collection system must be controlled to prevent loss of part of the sample. As an example of what may happen when excess velocities are used, a mixture of 50 pct coal and 50 pct limestone was crushed to —10 mesh and fed to a pulverizer equipped with an overhead dust-collection system. Fig. 4 shows the overhead dust-collection equipment used in this test. The pulverizer was set to give a product 95 pct —100 mesh in two stages. Velocity of air passing over the lip of the pulverizer was measured with an anemometer. After grinding, the finished product was analyzed to show the amount of calcium carbonate present. Fig. 3 shows graphically the increase in calcium carbonate as velocity through the dust-collection duct was increased. These data show that at a velocity of 1 ft per sec little if any of the coal was entrained by the overhead draft. At the maximum velocity, about 6.5 ft per sec, approximately 7 pct more coal was entrained than calcium carbonate. From an operating standpoint, this problem can be remedied easily by dampering the line to control velocity. The lowest velocity commensurate with satisfactory dust control should be used to prevent excess loss and, in some cases, selective dust loss. Collection of Dust in Laboratory Processes As in industry, the engineer desires to collect efficiently the dust produced by processes being investigated on a laboratory scale. However, in the collection of laboratory dusts he is faced with two additional problems: 1—The volumes of gas and the quantity of dust that must be recovered are small when compared with the capacity of standard dust-collector equipment, which must be scaled down in design except for collection of dust from large pilot-plant operations. 2—In addition, because of the variety of problems studied in the process laboratory, the engineer cannot design today a dust collector that will meet the conditions imposed by the processes of tomorrow. Sometimes, therefore, he must compromise collection efficiency to minimize the cost of fabrication and the amount of time diverted from the metallurgical to the dust-control problem. For collection of dust from laboratory processes a cyclone separator, filters, electrostatic separators, scrubbers, and settling chambers can usually be adapted for small-scale operations. The following

Jan 1, 1955

By T. Y. Yan

SUMMARY Laboratory high pressure column tests have shown that the presence of 1-20 ppm of aluminum ion effectively prevents permeability loss during uranium leaching with leachates containing sodium carbonate. If added after permeability loss has occurred, aluminum ion can restore the permeability to nearly its original value. No deleterious effect was observed on uranium leaching performance and the technique should be quite compatible with all field operations. INTRODUCTION The recovery of uranium values from underground deposits by in situ leaching or solution mining has become economically viable and competitive with conventional open pit or underground mining/milling systems (Merrit, 1971). In situ leaching processes are particularly suitable for small, low-grade deposits located in deep formations and dispersed in many thin layers. Many such ore bodies occur along a broad band of the Gulf Coastal Plain (Eargle et. al., 1971). The advantages of the in situ leaching processes have been reviewed (Anderson and Ritchi, 1968). In the in situ leaching process, a lixiviant containing the leaching chemicals is injected into the subterranean deposit and solubilizes uranium as it traverses the ore body. The pregnant lixiviant or leachate is produced from the production well and is then treated to recover the uranium. The resulting barren solution is made up with the leaching chemical to form lixiviant for re-injection. Upon completion of the leaching operation, the formation is contaminated with leaching chemicals and other species made soluble in the leaching operation and has to be treated to reduce the concentration of these contaminants in the ground water to levels acceptable to the regulatory agencies (Witlington and Taylor, 1978). Restoration is accomplished by injecting a restoration fluid, which could be the fresh water or water containing chemicals, into the formation. As it traverses the leached formation, the restoration fluid picks up the contaminants and is then produced at the production well. This produced water is either disposed or purified for recycle. In both phases of operation, formation permeability or well injectivity is one of the most important parameters which determines the viability of the in situ leaching process. Low formation permeability limits production rates, leading to uneconomical operations. The formation is said to be sensitive if there is a sharp loss of permeability on contact with water and other fluids. Many uranium bearing formations, for example, the Catahoula formation of the Texas Coastal Plain, contain significant amounts of clay minerals which are water sensitive. Serious permeability losses can occur when the pH and chemical composition of the lixiviant is significantly different from that of the formation water. Jones has investigated the influence of chemical composition of water on clay blocking of permeability (Jones, 1964) and Mungan studied permeability reduction through changes in pH and salinity of the water (Mungan, 1965). Various mechanisms of permeability damage have been proposed and reviewed (Jones, 1964; Mungan, 1965; Gray and Rex, 1966; and Veley, 1969). When large amounts of swelling clays are present, a significant fraction of the flow channels in the formation can be reduced due to swelling. However, in most cases, swelling need not be the main cause of permeability losses. Particle dispersion and migration or clay sliming can be more important causes for formation damage. Clay particles entrained in the moving fluids are carried downstream until they lodge in pore constrictions. As a result, microscopic filter cakes are formed by these obstructions, plugging the pores, effectively restricting fluid flow and reducing the formation permeability. Moore found that as little as 1-4 percent clays present in a fine grained sandstone could completely plug the formation if they are contacted by incompatible injected fluids (Moore, 1960). It has been found that injection of NaHC03/Na2CO3 lixiviant into formations with significant clay content often leads to loss of formation permeability and well injectivity. To alleviate this problem a change of the lixiviant composition to KHC03/K2CO3 has been proposed. At present, however, many in situ leaching operations employ NH4HC03/(NH4)2C03 mixtures as a source of carbonates. This approach has been successfully used in South Texas by Mobil, Intercontinental Energy, Wyoming Minerals and U.S. Steel, etc. The use of ammonium carbonates solutions, however, contaminates the formation and requires a time-consuming restoration operation. The other approach to reduce the permeability loss is to pretreat the sensitive formation with chemicals which prevent clay dispersion and migration. Such chemicals include hydroxy-aluminum (Reed, 1972 and Coppel et. al., 1973), hydrolyzable zirconium salts (Peters and Stout, 1977), hydrolyzable metal ions in general (Veley, 1969) and polyelectrolyte polymers (Anonymous). Still another approach, is to minimize the "shock" caused by sudden injection by gradually changing the chemical composition of the injected fluids from that of the formation water. THE APPROACH Since permeability loss can be an important factor limiting the efficiency and economic viability of the in situ leaching process, a study was initiated on

Jan 1, 1982

By F. H. Wilson, E. W. Palmer

Brass mills are familiar with a recurring problem which reveals itself during deformation of annealed metal as an opening up of cracks which are suggestive of a grain boundary pattern. A typical example is seen in Fig 1, which shows part of the convex surface of a cartridge brass disc which was slightly dished by the punching operation. Another illustration of the same type of defect was found in the surface of a finished cartridge case which split open on firing. These cracks, shown in Fig 2, were away from the split but indicate the presence of the type of weakness which permitted the splitting. Usually the weakness consists of separate cracks, the lengths of which are of the same order of magnitude as the grain size prior to the final anneal. Their typical appearance in a polished section is shown in Fig 3. This structure was found below the surface of a fractured tensile-specimen that had been cut from a large cartridge blank showing the defects on its convex surface. While the pattern formed by these cracks suggests a grain boundary origin, the cracks bear no relation to the currently existing grain structure. Thus Fig 3 shows that the grains have grown up to cracks already present. Since it is doubtful that the cracks were present in the metal before the anneal, they must have formed during the anneal but prior to recrystallization. The term "fire-cracking" has been generally applied to cracking that occurs during an anneal under the influence of internal stress, but refers more specifically to obvious macroscopic cracking attributable to the presence of a low melting phase, usually lead. Since the type of cracking described above may occur when the lead content is very low, we have considered it a somewhat different phenomenon, and have called it "inter-granular parting." While most examples involve cartridge brass, intergranular parting has also been observed in the fabrication of large seamless tubes from discs of both 85/15 red brass and 70/30 cupro-nickel. Similar cracking in nickel silver was investigated by Jones and Whitehead,1 who showed that it could occur during healing or cooling. That which occurred on heating they called "fire cracking," and they suggested that, a transformation at about 320°C might account for its occurrence. It was felt in this laboratory that the observed parting was probably one aspect of the general observation, first made by Rosenhain and Archbutt,2 that a tendency toward intergranular fracture under tensile stress increases with increasing temperature and decreasing rate of strain. In this case the stress involved would be internal. The rate of strain would be exceedingly slow, a localized internal creep. Reference to the literature uncovered no efforts to extend the observations of Rosenhain to conditions involving only internal stress. Accordingly, an exploratory research, sufficient in detail to satisfy us as to the probable truth of this explanation of the observed intergranular parting, was undertaken. The internal stresses present during the early stages of an anneal (prior to recrystallization) would be from two sources: residual stresses developed during deformation, and thermal stresses caused by uneven heating and expansion. Thermal stresses would vary widely according to shape, size and manner of heating, and can be considered as supplementary to residual stresses. It seemed necessary to determine the stress and temperature conditions under which parting would occur in a relatively short time, and then to establish whether or not in- ternal stresses may persist to an extent adequate to cause parting at such temperatures. (Jones and Whitehead1 and Moore and Beckinsale3 made tests which indicated that stress relief required an appreciable time.) During the course of the research the desirability of studying the effect of grain size became apparent, and this factor is one of the major variables of our investigation. Intergranular Parting under Tension at Elevated Temperatures In early experiments, hard 70/30 brass tensile specimens, with unknown residual stresses, held for 10 min. at applied stresses from 30,000 to 40,000 psi at temperatures from 300 to 350°C, showed no macroscopically visible cracks when unloaded and cooled, but cracks very similar in appearance to those observed in commercial practice were revealed in these specimens by pulling them to fracture. Annealed specimens, on the other hand, showed no cracks in such experiments, apparently because they deformed plastically at stresses below those necessary to cause parting in a reasonable time. Hence, the specimens used for this study were first strengthened by cold tensile elongation, giving them an unavoidable residual stress pattern (determined largely by grain size and orientation) which would, however, correspond in direction, at least, to the stress pattern obtained under stress at temperature. A variation in these residual stresses might be expected with variations in grain size, but following any given anneal the reproducibility of stress pattern should be as good as that of the grain size measurement. With no information as to the effect of the amount of prior deformation, tests were conducted on specimens given the same cold elongation, using a stress applied at temperature which was a constant proportion of the stress required to produce this elongation. In

Jan 1, 1950

By J. R. Elenbaas, J. A. Vary, D. L. Katz

The development of gas fields, oil fields and aquifers for storing natural gas is treated from two main vieu.-points: (I) the volumetric storage capacity for gas in a given situation and (2) the prediction of the number of wells required for the delivery of gas. Other experiences in the design and operation of storagc fields are incluclerl INTRODUC TION Storage of natural gas in underground reservoirs near the terminus of long distance pipelines has been the prime factor in opening the space heating market to the natural gas industry. Storagc has permitted a major. increase in both the load and the load factor of pipe-lines; some are now operating at steady load throughout the year. Thus, underground storage has been responsible for the rapid increase in demand for natural gas in recent years. Three types of reservoirs have been used for gas storage: natural gas reservoirs, oil reservoirs, and waterbearing sands or aquifers. This paper presents the factors to be considered when developing gas storage reservoirs of these three categories. There are two prime considerations tor any storage reservoir: (1) the volume of gas which a given reservoir will store advantageously and (2) the number 01 wells needed to provide the required peak deliverability. These two problems will be considered for the three types of reservoirs just noted STORAGE IN PARTIALLY DEPLETED GAS FIELDS Early storage operations consisted of replenishing the natural gas in a depleted gas field situated adjacent to the market. Today, newly discovered fields near the market may be considered for storage, and this discussion applies equally to both types of reservoirs. For reservoirs originally containing gas or oil, the question of the impermeability of the cap rock nor-mally does not arise. However, such fields are likely to have many wells drilled either to or through the reservoir under consideration. Positive assurance must be obtained that such wells are or can be made mechanically tight. Corroded casings may need to be lined or permanently plugged. Abandoned wells should bc reopened and properly cemented. The volumetric capacity for gas storage depends upon space available in the porous rock as well as pressure and temperature of the gas in the reservoir. The production-pressure decline data on partially depleted gas reservoirs without water drive permit calculation of the reservoir space for gas. Isopachous maps of sand volume and porosity data for the reservoir rock provide an alternate method of calculating the pore volume for water-drive reservoirs. The pressure range selected for the storage cycle depends upon ()) the safe upper limit of pressure. 2) the flow capacity of wells and (3) compression requirements when injecting gas into the reservoir or delivering to market. Normally, gas and oil fields have pressures at discovery in the range of 0.43 to 0.52 psi/ft of depth. Pressures of around 1.0 to 1.2 psi/ft of depth appear to lift the overburden1-3 and invite uncontrolled movement of fluids in the porous rock. Some top pressure is normally selected for a storage reservoir ranging from below discovery pressure for deeper reservoirs to 0.65 psi/ft of depth for shallower reservoirs. Pressures to 0.66 psi/ft have been experienced without difficulty. The lower pressure limit is set by water intrusion accompanying low pressures, reduced flow capacity for wells at lower pressures and compression requirements. Depletion-type gas reservoirs often encounter water problems in the later stages of gas production. Such water intrusion may be due to movement from the surrounding aquifer. Accordingly, displacement of this water back into the aquifer by gas pressure and subsequent surges of water corresponding to the gas storage pressure cycle must be considered. Storage fields often produce in four months a volume of gas equal to its initial content. Rapid decreases in reservoir pressure occur, such as 20 psi/day. Accordingly, closed-in pressure observation wells which reflect the pressure in the bulk of the reservoir are required for following the operation of the reservoir. It has been found that a plot of observation wellhead pressures against gas content, Fig. 1, is very useful in observing operation of the field, checking the inventory and predicting future behavior. The plot is based on a given quantity of base or cushion gas in place. The injection and withdrawal curves may spread depending upon the homogeneity of the reservoir rock. permeability of the rock, well spacing and flow rates.

By P. M. Robinson, J. S. LI. Leach

The heats of solution oj&apos; indiurrr, tin, lend, nrzd tellurium have been calculated from the measured heat effects when mechanical mixtres of indium and telLuium tin and tellurium, and lead and tellurium were added to liquid bismuth. The results are in good agreement xith publislzed values.s for the separate sollction of each eleltzent in bismuth. The heats oj solution of cadmium and tellurium calculated from the rneasuved heat effects on adding trechanical mixtures of these elements do not ugree zc,itl the published values jbv the separate solution of each element. It is shown that at 623°K Ile interaction between cadmium and tellurium dissolved in liquid bismuth is strong enough to led lo preciPitation of solid CdTc. The heats oj- jor-mation of CdTe at 273" nd 623°K (1)-c crilculated fi-or the measured heat ejlfecls. The calcnlaled az&apos;erage deviation from the Kopp-l\&apos;ez?,zunrz rule fov solid CdTe is less than 0.06 cat per g-atom- C over this lertzperalure range. Tlze importance 0.f these oDserl.ations to the determination of heals of formation hy metal solution calorimetry is considered. LIQUID metal solution calorimetry is a convenient method for determining the heats of formation of solid compounds. In this technique the heat of formation is the difference between the measured heat effects on dissolution of the compounds and of mechanical mixtures of the components in the liquid metal.&apos; The heat of solution of the mechanical mixture may be calculated from the measured heat effect. At infinite dilution of the solutes, this heat of solution is equal to the sum of the heats of solution of the separate components. If the heat of solution of one of the components is known, the value for the other can be derived; if both are known, they may be used to check the accuracy of the calorimetric technique. The heats of formation of the tellurides of cadmium, indium, tin, and lead have recently been measured by metal solution alorimetr. The heats of solution of indium, tin, lead, and tellurium at infinite dilution in liquid bismuth at 623"K, calculated from the measured heat effects on solution of the mechanical mixtures, are in good agreement with the published values. The heats of solution of cadmium and of tellurium calculated from the measured heat effect on solution in bismuth at 623&apos;K of mechanical mixtures of cadmium and tellurium, however, do not agree with values estimated from the literature. 1) EXPERIMENTAL PROCEDURE AND RESULTS The Heats of Solution of Indium, Tin, Lead, and Tellurium in Bismuth. The heat effects were measured when mechanical mixtures corresponding to the compounds In,Te, InTe, In2Te3, In2Te5, SnTe, and PbTe were dissolved in bismuth. The calorimetric procedure and the method of calculation have been described elsewhere.&apos; The heats of solution of the mechanical mixtures were obtained by subtracting the change in heat content per gram-atom of the sample between the addition temperature (273°K) and the bath temperature (623"K), (H623°K - H273°K)S, from the measured heat effects. The calorimeter was calibrated with pure bismuth. The reported values of the measured heat effects are based on (HGoK - ^273oK)Bi = 4.96 kcal per g-atom.3 The measured heat effects are found to be linear functions of the solute concentrations of the bath in the dilute solution range. The values, extrapolated to infinite dilution, are listed in Table I, together with the heats of solution of the mechanical mixtures calculated using the published values of (H 623°K - H273°k)s for indium, tin, lead,3 and tellrium. All the error limits quoted in this work represent the spread of values obtained. The heats of solution in liquid bismuth at 623°K of mechanical mixtures of indium and tellurium in four different proportions were determined. Values of the heats of solution of the two components were then calculated from the resulting four simultaneous equations: The heats of solution at infinite dilution of tin and lead in liquid bismuth at 623°K were calculated from the heats of solution of the mechanical mixtures of tin and tellurium and of lead and tellurium using the heat of solution of tellurium calculated above. These values of the heats of solution are listed in Table I1 together with some published values for comparison.

Jan 1, 1967

By S. G. Epstein

Using the capillary-reservoir technique, electromi-gvation rates of cadmium and indium in liquid bismuth were measured at several temperatures. The electric mobility of cadmium Jrom 305° to 535°C and indium from 310° to 595°C can be expressed as a function of temperature by the equations UIn = 1.52 x 10-3 exp sq caz per v-sec Migraion of both solutes was cathode-divected at a rate rnore than four tiMes tHAt previously found for siluer in liquid bisnmth. The electric mobilities of cadmium and indiulrz in liquid bismuth at 500° C are nearly identical with their respective mobilities in mercury at room temperature. AS part of a systematic study of the variables which are considered to control electromigration in liquid metals, the electromigration rates of cadmium and indium in liquid bismuth have been measured. Mass transport properties of silver in liquid bismuth have been reported previously,&apos; and measurements of tin and antimony in liquid bismuth are forthcoming. Comparisons will be made with literature values for these same solutes in mercury.2&apos;3 This series of solutes was selected to determine the effect of the solute valence on its electromigration. Silver, cadmium, indium, tin, and antimony have nearly equal atomic masses but have chemical valences ranging from +1 to +5. They are all fairly soluble in bismuth above 300°C and all have radioactive isotopes, which are an aid in making analyses. EXPERIMENTAL TECHNIQUE Electromigration of cadmium and indium in liquid bismuth was measured by the modified capillary-reservoir technique previously described.&apos; In this method irradiated cadmium or indium is added to bismuth to form alloys containing about 1 wt pct solute (<2 at. pct solute). Several quartz or Pyrex capillaries: 1 mm ID and 5 cm long, vertically oriented, are simultaneously filled in the reservoir of the liquid alloy. A direct current is passed through two of the capillaries, which contain tungsten electrodes sealed in the upper end. The other capillaries sample the reservoir during the experiment. After a measured time interval the capillaries are removed from the reservoir and rapidly cooled. The glass is then broken away from the solidi- fied alloy, which is then weighed, dissolved in acid, and analyzed for solute content by chemical and radiochem-ical techniques. An electric mobility (velocity per unit field) can be calculated from the amount of solute entering or leaving each capillary by the simplified expression1 in which Ui is the electric mobility of the solute, ?mi the solute weight change, Ci the solute concentration of the reservoir, I the current, p the alloy resistivity, and l the duration of the experiment. This expression is valid as long as the experiment is terminated before a concentration gradient develops across the capillary orifice. Earlier experiments showed that the concentration gradient formed initially at the electrode changes with time and eventually reaches the orifice, due to back-diffusion. This condition produces a solute exchange between capillary and reservoir by diffusion or convection, opposing the electromigration, which results in a lower measured value for the electric mobility. To determine if the concentration gradient had reached the orifice, the capillaries used in some of the experiments were sectioned at 1-cm intervals and the solute content of the alloy from each section was radiochemically determined. A typical concentration profile for an experiment with indium in bismuth is shown in Fig. 1; cadmium in bismuth showed similar behavior. As illustrated in the graph, very little back-diffusion has occurred in the capillary containing the cathode, since the concentration gradient is confined to the upper 1 cm of the capillary. In the capillary containing the anode, however, the concentration gradient is much broader, extending nearly to the orifice, even though the net change in solute concentration is nearlv the same in both capillaries. Since cadmium and indium probably lower the density of bismuth when alloyed, depletion of the solute from the alloy adjacent to the anode would increase the density of the liquid in the uppermost region of the capillary. This would give rise to convective mixing within the capillary, causing the broadened concentration gradient. Conversely, the alloy adjacent to the cathode should have a reduced density as the solute concentration is increased by migration, explaining the "normal" concentration profiles found in these capillaries. This disparity was not found for electromigration of silver in bismuth. Both metals have similar densities at the operating temperatures, and nearly symmetrical concentration profiles were found in the two capillaries of each exueriment. This density effect was also apparently encountered when an attempt was made to measure diffusion coefficients for indium in liquid bismuth by the same technique which was successfully used to measure diffusion of silver in bismuth.&apos; Capillaries 1 mm ID and 2 cm

Jan 1, 1968