Search Documents

By D. A. Elgillani, M. C. Fuerstenau

In this paper, oxidation potentials measured in the presence of various concentrations of cyanide, ferro-cyanide, and ferricyanide and ethyl xanthate at various values of pH are related to flotation response. Eh-pH diagrams are presented to show that the formation of surface ferric ferrocyanide is probably responsible for depression when cyanide is added. The influence of cyanide on the depression of pyrite with xanthates as collector has been the subject of a number of investigations,'-6 and several theories on the mechanism of depression have evolved from these studies. Wark and Cox7 and Gaudin8 have suggested that the depressing effect is due to a competition of cyanide ion with xanthate ion for the surface. Cook and his colleagues9-11 have explained this phenomenon in terms of competition between hydrocyanic acid and xanthic acid. Sutherland 12 has shown that although both of these theories accurately describe the relation between pH value and cyanide addition at constant collector addition, they fail to describe the relation between pH value and the amount of collector required to cause flotation. Taggart 13 suggested that depression in these systems is due to the formation of a reaction product between ferric ion at the pyrite surface and ferrocyanide ion derived from solution. Majumdar4,6 has attempted to prove this hypothesis by measuring the contact angles of pyrite in the presence of 25 mg per liter ethyl xanthate and different concentrations of potassium ferrocyanide and ferricyanide. In all cases the contact angles were quite high up to pH 10. These results indicate that pyrite should not be depressed by either potassium ferrocyanide or ferricyanide. In view of these facts, Majumdar has assumed that the compound Fe(CN)2 forms at the surface. Gründer and Bornl4 have stated that depression may be due to the formation of the compound K2Fe(II)Fe(CN)6 at the pyrite-solution interface. This compound is thought to be an interaction product between the K2Fe(CN)6-2 ion from solution and the Fe++ ion at the pyrite surface and, accordingly, K4Fe(CN)6 should depress pyrite at least as effectively as KCN. This was proven experimentally, but there was no simple relation between the depression of pyrite and the concentration of either KCN or K4Fe(CN)6 in solution. In view of the many mechanisms that have been proposed for pyrite depression by cyanide, it is apparent that a clear understanding of the phenomena occurring in these systems is lacking. One reason for this may be the fact that the species responsible for pyrite flotation in the presence of xanthate is not the xan-thate ion but rather dixanthogen.15 Since the oxidation of xanthate to dixanthogen is dependent on the oxidation potential of the solution, it would seem that knowledge of these potentials would be a requisite to understanding the pyrite-xanthate-cyanide system. It is the object of this paper to measure both the oxidation potential and pH of the pyrite systems in the presence of various concentrations of cyanide, ferrocyanide, and ferricyanide and xanthate and to relate these values to flotation response. EXPERIMENTAL MATERIALS AND 'TECHNIQUES In the experiments discussed here, pure potassium ethyl xanthate was used as collector, and reagent grade potassium cyanide, potassium ferrocyanide, and potassium ferricyanide were used as depressants. Reagent grade HC1 and KOH were added for pH adjustment. Conductivity water, made by passing distilled water through an ion exchange column, was used in all experimental work. Two natural samples of pyrite were used in the investigation. Sample preparation for flotation included dry grinding with a mortar and pestle and sizing the product to 100 x 200 mesh. Prior to flotation, a 0.75-gm sample of pyrite was added to a solution containing a known amount of depressant at the desired pH value, and the system was conditioned for 4 min. Following this, a known amount of collector was added and the system was conditioned for another 4 min. The pH — termed flotation pH - was measured; the pulp was transferred to a Hallimond cell, and flo-

Jan 1, 1969

By C. E. Ells, A. Sawatzky

The effect of neutron irradiation on tensile properties of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy has been evaluated for integrated neutron fluxes up to 3 x 1020 n per sq cm (E > 1 Mev). Specimen temperature during irradiation was normally 300°C. The material was studied both in annealed and in quenched and aged conditions. When the alloy (fab-ricatedfrom sponge zirconium) is quenched from a temperature =40°C below the a + ß/ß transformation and aged 6 hr at 535oC, neutron irradiation up to the maximum studied has little effect 071 reduction in area, although there is a drop in uniform elongation and the yield strength is increased by = 25 pct. Conversely, irradiation of the alloy in an annealed condition can result in much greater changes in properties, with yield-strength increases of up to 200 pet. The dose dependence of irradiation hardening obeys the saturation equntion proposed by Makin and Minter to explain hardening in copper and nickel: Act = C[1 - exp(-Døt)/1/2 A rnodel is proposed to explain the effect of niobium content and metallurgical condition on irradiatiotz behavior. THE Zr-Nb alloys form a class of material susceptible to marked strengthening by quench and age heat treatment. With niobium concentrations as low as 2.5 wt pet, strengths can be developed which are double those of annealed zircaloy-2.1 Since the neutron-capture cross section of the Zr-2.5 wt pet Nb alloy is nearly identical to that of Zircaloy-2, significant gains in power-reactor neutron economy could be obtained by replacing stressed in-reactor components of Zircaloy-2 with the heat-treated Zr-Nb alloy. When the solution heat-treatment temperature is in the high (a + ß) phase, then the tensile properties of the quenched (and aged at 500°C) material have been shown to be relatively insensitive to neutron irradiation.1-3 Addition of small quantities of copper to the binary Zr-2.5 wt pet Nb alloy gives a useful reduction to the corrosion rate in air and carbon di- oxide,&apos; and a ternary alloy of composition Zr-2.5 wt pet Nb-0.5 wt pet Cu was chosen for one component in the Douglas Point Reactor. This application utilizes both the corrosion resistance to a moist air-carbon dioxide environment and the strength developed by a quench and age heat treatment. By suitable choice of solution heat treatment and aging temperatures, tensile properties of the ternary alloy can be made nearly identical to those considered as optimum for the binary alloy. One effect of the copper addition, however, is to give marked changes in the aging kinetics of the alloy.&apos; For this reason, it appeared that neutron irradiation might promote overaging in the ternary alloy, particularly at the elevated service temperature (=300°C). This paper describes the effect of neutron irradiation on the tensile behavior of the Zr-2.5 wt pet Nb-0.5 wt pet Cu alloy in several metallurgical conditions pertinent to its use as a reactor material. The metallurgical conditions included those for which aging occurs in the unirradiated material, and fully annealed conditions for which a higher degree of thermal stability could be expected. 1) EXPERIMENTAL Two batches of alloy were used, both made from sponge zirconium. The fabricator&apos;s analysis of principle constituents showed no significant difference between the two batches, Table I. The rod material was rolled to 1.5 in. diam, and then swaged to final sizes of 0.5 to 0.375 in. diam at nominal temperatures of 785" and 625°C for the AM and AS batches, respectively. Subsequent hydrogen analyses at CRNL confirmed that the hydrogen concentration of the as-received rod was indeed <20 ppm. However, it was found that the (a + ß)/ß transus for the AM material was approximately 25°C lower than that of the AS material, indicating rather more difference in oxygen concentration than given in Table I. Except for a small difference in yield-point behavior, the tensile prop-

Jan 1, 1965

By P. R. Smith, R. A. Walters

Borates have been mined in the desert areas of California and Nevada for more than 100 years. To about 1890, playa surface mining provided the chief sources of boron minerals. Underground mining of colemanite and later of borax and kernite was predominate until about twenty years ago. Open pit mining of the large deposits of borax and kernite near Boron, California has been most significant for the past twenty years. Mining of colemanite in the Ryan, California area, near Death Valley, began in 1907. Following the discovery of the large deposits in the Boron area (about 1957), mining in the Death Valley area became nearly nonexistent. Only small tonnages were mined for special uses. Little mining was done in the Boraxo area near Ryan. The first claim was made in about 1915. In 1960 the area became the property of the Kern County Land Company, which was acquired by Tenneco Oil Company in 1967. In 1976 the various boiate properties and claims in this region were acquired by American Borate Corporation. The open pit mine is now approximately 122 m (400 ft) deep, 910 m (3000 ft) long and 305 m (1000 ft wide). The borates in the Boraxo pit consist primarily of three minerals. These are about 50% colemanite (CB6011 5H20), about 40% probertite (NaCaB50g 5H20), and 10% ulexite (NaCaBgOg 5H20). The colemanite, along with boric acid and high-grade colemanite ore from Turkey provide the only sodium-free borates for production of textile grade fiberglas. When heated to its decomposition temperature, colemanite decrepitates to a fine powder, which is the basis for the concentration process. The gangue minerals in this deposit are primarily calcite and clays, including bentonite. The ore body has a very low arsenic content, which is a desirable feature. Test work had been done with samples prior to the results discussed herein. This paper will discuss results of test work which were the basis for erection of a plant, and the subsequent plant operations. Laboratory Calcination and Air Tabling Tests Laboratory calcination tests showed that substantial upgrading of the borate could be accomplished by calcining followed by screening of the calcined material. Removal of the + 28 mesh calcine resulted in borate losses of less than 10% with a rejection of 40 weight % or more of the calcine. The minus 65 mesh calcine generally met the requirement of containing 48%, or more, B203. The minus 28 plus 65 mesh material contained an intermediate quantity of borate and would require additional treatment. Testing demonstrated that ore would not have to be reduced to a size finer than 19 mm (3/4 in.) prior to calcination. A temperature range from 400 to 455OC (750 to 850°F) was apparently satisfactory. Calcination at a temperature of 48Z°C (900°F), or higher, was unsatisfactory due to fusion. All laboratory calcination tests were static tests conducted by placing small covered charges in a laboratory furnace for 40 min. In all tests vapor issues from the furnace for 5 to 7 min. Following this period the ore could be heard "popping," due to decrepitation of the colemanite. The reaction generally continued for approximately one-half hour. Various size fractions of the calcination products from laboratory tests were subjected to laboratory air tabling tests, usually after removing the plus 28 mesh material. Laboratory air tabling tests were conducted employing a Whippet V-80 model air table manufactured by Sutton, Steele and Steele Co. now known as Tripple S Dynamics. Variables include both end and side-tilt, speed of vibration, and quantity of air rising through the deck. In addition to the variables in the machine itself, the feed rate is also a rather critical variable. Testing demonstrated that all - 28 mesh size fractions of the calcine could be successfully concentrated to 48% F2O3 or greater. For the finer material recoveries into the concentrate were between 85 and 90% of the borate. With the coarser material a substantial amount of middling was produced which required cleaner tabling. Laboratory calcination and air tabling tests indicated a process whereby the borate could be concentrated to about 50% B203 with borate recoveries approaching 90%. Moreover, the iron content of the concentrate was well below the required specification of 0.3% Fe2O3. Pilot Plant Calcination Following the laboratory test work described above, pilot plant testing was conducted to prove the process, provide data for engineering studies, and provide product for a prospective purchaser. The kiln used was 0.9 m-diam (3 ft) by 9.0 m (30 ft) long and had a belly section 1.2 m-diam (4 ft) by 2.74 m (9 ft) long near the discharge end. The kiln was operated at a speed of 0.7 rpm. Gas was fired into the kiln at an average rate of 27.1 m3/hr (958.4 cu ft per hr). The air to gas ratio used was 10:1. The ore was fed to the kiln countercurrent to the flame and discharged through a hopper into a screw conveyor which discharged to a 1.2 m (48 in.) Sweco separator. The separator had 28, 65, and 150 mesh screen cloths, with the plus 28 mesh fraction being discarded. The minus 28 mesh fractions were later subjected to air tabling. The exit gases, containing some calcine dust, were swept through two cyclones to recover the dust. The gases then were scrubbed in a Ducon scrubber; very little dust reported past the first cyclone. The dust from the first cyclone was also saved in drums. In addition to the gas rate, the flue gas velocity, after

Jan 1, 1981

By C. Wert, G. Mah

A relaxation peak thought to be due to the presence of C-C pairs in cobalt has been observed. It exists both above 420"C, where cobalt has the fcc structure, and below 420"C, where cobalt has the hcp structure at equilibrium. The effect is thought, however, to be caused by motion of C-C pairs in the fcc phase in both instances; enough retained fcc phase was deduced to be present at temperatures below 420°C to make the phenomenon possible. Measurements of the aniso-tropy of the effect in single crystals of various orientations of fcc phase showed the effect to have a maximum value in longitudinal strain for a [loo] crystal and a minimum value for a [Ill] crystal. This observation seems to rule out the possibility of (110) nn pairs being responsible for the effect. From measurements of the strength of the relaxation in the alloys, we reach the conclusion that both the binding energy of the pairs and the specific relaxation per pair are smaller than corresponding quantities for interstitial pairs in bcc metals. DETERMINATION of the details of atom placement of small atoms such as carbon, nitrogen, oxygen, and hydrogen in metals has been a difficult problem. In certain alloys such as martensite extensive departure from random placement of the interstitials can be deduced from X-ray diffraction off the atoms of the host metal, but such diffraction techniques are of small help for small departures from randomness. A technique which does offer promise in the latter instance is the anelasticity of these interstitial alloys. Most previous investigations using this property have utilized alloys in which the solvent is one of the bcc metals, alloys such as These studies have been interpreted to show that an interaction exists between interstitials which causes them to form clusters in more than random numbers; the binding energy of interstitials in such clusters has been deduced to be about 0.1 ev per atom (for small clusters of size two to four atoms). Similar investigations have been carried out on close-packed solvent metals, Ni-C by and Diamond and Ag-O by Papazian.8- In both of these svstems. no relaxation of the singly dissolved interstitial is expected, so an-elastic behavior of the interstitials must be caused by their association in some cluster or complex of non-cubic symmetry. Since relaxations in these alloys were observed to have a strength which varied about as the square of the interstitial concentration, the effect was deduced to be caused predominately by motion of i-i pairs in the crystal. A striking difference is observed in relaxation strength of interstitial alloys between the bcc and fcc systems. The specific effect per interstitial atom is much larger for the alloys in the bcc crystals than for those in fcc crystals. Comparing clusters of size two in the Nb-O system4 and the Ni-C system,7 one finds the magnitude of the anelastic effect per interstitial atom in the former to be some 100 times greater than that in the latter. Such a difference in relaxation strength might be caused by a difference in concentration of the pairs (this means a higher binding energy in the bcc crystals). It might also be caused by a large difference in shape factor of the elastic strain field about the pairs between the two cases (a much more noncubic shape factor would be required for the bcc crystals). This investigation was undertaken to examine the possibility of C-C pair formation in alloys of cobalt and carbon using anelastic effects. Since cobalt has both fcc and hep phases, it seemed to offer the chance that measurements over a range of frequency might permit comparison of properties of pairs in the two crystal types. Although this goal was not reached, several significant facts were deduced from the observations. 1) An anelastic phenomenon believed to be associated with the presence of C-C pairs in cobalt exists. It has many features in common with that observed in nickel. 2) The effect is thought to be caused by pair motion in the fcc phase. 3) Calculations of the relaxation strength A, which includes as a parameter the product of the pair concentration, C, and the square of the shape factor &apos;, show that this parameter is much smaller in the CO-C alloy system than in the interstitial alloys in the bcc systems. 4) From this finding, we reach the conclusion that both the binding energy of C-C pairs in cobalt and the specific relaxation strength per pair are small compared to corresponding values for such pairs in the bcc systems. 5) The crystalline anisotropy of the effect permits the identification of reasonable geometrical models of close C-C pairs. I) EXPERIMENTAL PROCEDURE A) Method of Measurement. The anelastic measurements-—all of which were constant frequency measurements of internal friction—were designed to study the expected phenomenon in both the hcp and fcc structures in cobalt. Knowledge of similar measurements in Ni-C alloys led us to believe that the damping peak should occur below the transformation temperature for frequencies near 1 cps and above for frequencies near 100 kcps. This surmise was correct. The low-frequency measurements were made on wire specimens using a vacuum torsion pendulum; the damping peak was found at about 2&apos;70°C at a frequency of 1 cps. Because of large superimposed damping of magnetic origin at this temperature, a longitudinal magnetic field of about 1500 oe was applied to the

Jan 1, 1969

By O. F. Walker, W. C. Hahn, V. A. Johnson, J. D. Wood

The diffusion coefficients of zinc in single-crystal zinc and carbon in single-crystal and poly crystalline nickel were measured by means of radioactive tracer techniques both with and without the application of ultrasonic vibrations under conditions such that the temperature of the sample was closely controlled. The results of this investigation indicate no enhancement of diffusion in any of the samples. It is suggested that previously reported enhancement may have been due either solely to temperature increases caused by ultrasonic vibrations or in combination with changes in the boundary conditions. A number of observations have been reported in the literature in which it has been implied or inferred that the application of ultrasonics enhances diffusion (see, for example, Refs. 1-5). The present study was undertaken in an attempt to observe this effect under carefully controlled conditions, particularly with regard to measurement and control of the temperature of the sample. Two different types of systems were studied; these were the self-diffusion of zinc and the diffusion of carbon in nickel. EXPERIMENTAL For diffusion with ultrasonic energy applied, the samples were included as part of a resonant ultrasonic system operating at 58.5 kcps. The ultrasonic generators used were rated at 100 and 250 w and could be tuned over a frequency from 10 to 100 kc. A PZT (lead titanate/lead zirconate) ceramic transducer provided the driving vibration. This system requires no metallurgical joining of the specimen to the acoustical transmission line since the ultrasonic driver and the follow-up section clamp the specimen in position by means of a constant pressure of 50 lb developed by an air cylinder. The ultrasonic driver and follow-up section, both made of titanium, were 4 in. in length from clamping point to the end in contact with the specimen. Using the relationship given by Mason,6 A = V/f, the resonant wavelength, A, in titanium is calculated to be 3.3 in. at a frequency, f, of 58.5 kc, taking the velocity of sound in titanium, V, as 1.95 X 105 in. per sec. The 4-in. driver and follow-up section, therefore, are each 4.0/3.3 =1.21 times the resonant wavelength. Clamping pressure must be applied at stress nodes of the transmission line in order to preserve resonance. Therefore, a specimen length of 0.58 times the wavelength in the specimen was required to place the clamping pressure application points at stress nodes exactly three wavelengths apart. A stress antinode was contained in the center 3 in. of the specimen. A small PZT ceramic disc attached to the follow-up section provided an output voltage proportional to the intensity of the standing wave. This output voltage was monitored on an oscilloscope and the ultrasonic system was tuned to resonance by varying the frequency until the output signal was a maximum amplitude. The amplitude of the output signal was maintained constant throughout the diffusion anneal. A split cylindrical stainless-steel chamber, which was purged with argon prior to and during the runs, was placed around the specimen. The chamber in turn was surrounded by a movable furnace whose temperature could be controlled to 7C. Heat exchangers were used to cool the driver, follow-up section, and ultrasonic transducer. Great care was taken to obtain the true specimen temperature in all cases. Several different methods were tried; the most successful was that in which the thermocouple was held in contact with the midlength of the specimen by means of an asbestos insulating pad and wire straps. In the case of zinc, single-crystal specimens of 99.999 pct purity were used. The samples were 0.25 by 0.25 in. square and of the proper length for resonance, that is 1.1 in. long with the c axis parallel to the long dimension of the specimen for the case of diffusion perpendicular to the c axis and ultrasonic motion parallel to the c axis, and 1.9 in. long with the c axis perpendicular to the long dimension of the specimen for the case of diffusion parallel to the c axis and ultrasonic motion perpendicular to the c axis. In each case, one of the rectangular faces was electroplated with a thin film of zinc containing Zn The constant pressure used to clamp the specimen in place in the ultrasonic system caused some deformation in some of the samples. For these samples the deformation was concentrated in either end of the specimen; thus, for all samples (both zinc and nickel) the center in. was cut from the specimen after the diffusion anneal to be used for sectioning and counting. The nickel single-crystal samples, of 99.999 pct purity, were used in the form of rods 0.25 by 0.187 by 2.07 in. long with the (100) direction parallel to the rod axis. The polycrystalline nickel samples of 99.97 pct purity had an average grain diameter of 0.007 in. and were used in the form of rods 0.25 by 0.125 by 1.87 in. long. The direction of ultrasonic motion was parallel to (100) direction (bar axis) for the single-cqstal samples and parallel to the bar axis for the polycrystalline specimens. A thin film of c14 suspended in methanol was applied to the diffusing face of the specimen. Two specimens were butted together lengthwise for each diffusion anneal to minimize oxidation. After diffusion, a precision lapping device similar to the one described by Goldstein7 and a radiation detector were used to obtain a plot of specific activity vs penetration distance for each specimen. (A scintil-

Jan 1, 1969

By C. F. Allen, G. B. Walker

K. F. TROMP*—In dealing with the question of the most suitable kind of solid media for heavy density suspension processes Walker and Allen point out that the particle size of the solid media should not be taken too fine, as the viscosity increases with the area of the solid media and a low viscosity is essential lor high tonnage and accurate separation. A coarser particle size of the solid media will, in their opinion, of necessity give rise to a differential density in the bath (higher gravity at the bottom of the bath than at the top) but they advocate acceptance of the differential density rather than a higher viscosity. Though I fully agree with the choice the authors have made, I cannot subscribe to their view that only by accepting a differential density in the bath a coarse particle size of the solid media can be used. There certainly is another alternative: stronger agitation. Applying sufficiently strong vertical currents, a uniform gravity can be obtained quite well in a suspension of a coarse solid media. Of course, this is not a very attractive solution, for it means a degradation of the true gravity separation and a step backwards to hydraulic classification, which makes the washing dependent on size and shape of the particles. However, to a greater or lesser extent, this is what actually takes place in all the heavy density suspension processes relying on a uniform gravity in the bath. The so-called "stable" suspension processes make no exception. They all "stabilize" their suspensions by introducing or creating vertical currents, be it upwards or downwards or both, be it by hydraulic or by mechanical means. In fact, there is no such thing as a "stable" suspension in gravity separation, as the very reason for the use of suspensions in this field is the property that the solid media is able to settle and so facilitate the recovery. I have been enlarging on this point because the characteristics of the various processes can only be well understood and viewed from the same angle (from Bar-voys up to Chance) when the fact is recognized that mechanical or hydraulic agitation is a condition sine qua non for obtaining a uniform density from top to bottom in a suspension. Is a Cone-slraped Vessel Essenlial? Of the two alternatives for getting a low viscosity Walker and Allen have preferred correctly the sacrifice of uniform gravity in the bath instead of increasing further their vertical current arid agitation. The resulting differential density of the bath brings the problem of bow to prevent accumulation of intermediate gravity products in the bath, an accumulation which, if not prevented, would ultimately plug their cone. According to the authors an open-top cone combined with a downdraft current of the bath liquid would he the only suitable way to cope with such suspensions and they assume as a fact that "in any vessel other than a cone, such a differential density could not be tolerated." My experience is quilt: different. In my process, which has been in successful operation for more than a decade, differ-ential density of the suspension is applied ranging from values below 0.1 up to differentials above 0.5, according to the prevailing requirements of the individual plant. In this process, which is charac-terized by the use of horizontal currents in a suspension of differential density, the form of the vessel is of secondary importance and different types are in operation. It so happens that none of these are in the, form of a cone. The fact that 24 washboxes on my process have been installed and 12 others are under construction may constitute sufficient proof against the opinion that only a cone-shaped separator would be suited for differential density separation. Horizontal Currents in Differentia1 Den-sity Sepparation I myself have some doubts as to the suitability of a cone with downdraft for dealing with differential density (or, for that matter, any other washbox relying on vertical currents for removing the intermediate gravity products). It ap-pears to me that it is restricted to feed of small size only and even then with watch-fulness. If we take, for example, a piece of 2 in., the draft necessary to pull such a piece down to a zone wherein the den-sity of the suspension is, say, 0.03 higher, is quite considerable. For a suspension of, say, 1.6 sp gr the downdraft will have to be in the region of 3 in. per second. Unfortunately. most of the differential in density is in the part immediately below the reach of the top current which transports the floats. Consequently, we need the downdraft where we like it least: in the upper part of the cone. This entails the risk that light float particles are carried away with the downward current. This current of, say again, 3 in. per second would carry particles up to 1.3 sp gr and 3/8 in. size into the 1.6 gravity zone. This is prohibitive. It is also prohibitive because a downdraft of 3 in. per second in the upper part of the cone would require a tremendous circulation of medium. IIalf way up a 20 ft diam cone, a downdraft of 3 in. per second would correspond with 8500 gpm. With the downward current following the way of least resistance, the strength of the downdraft will not be exactly the same at different places of a cross area. If, as I anticipate, the center of the cone is favored, the strength of the downdraft will fall below the critical value near the

Jan 1, 1950

K. T. Aust and J. W. Rutter (General Electric Research Laboratory)—We find it difficult to reconcile the activation energies determined by Gifkins with his general conclusion that "migration during both creep and grain growth can thus be treated on the basis of the same model" (that of Lucke and Detert). Gifkins finds the activation energy for grain boundary migration during creep to be 24.5 kcal per rnol and that for grain boundary migration during grain growth to be 7.5 kcal per mol. The calculation carried out by Gifkins of the activation energy for grain boundary migration during grain growth, using the Lucke and Detert model, gives a value of 20 to 24.5 kcal per mol, rather than his experimental value of 7.5 kcal per mol. The theory of Lucke and Detert was developed to account for the rates of migration of grain boundaries in the presence of impurities during grain growth. The theory does not take into account the effect on the boundary migration of another, simultaneous process such as creep deformation and would be expected, therefore, to be applicable only to migration during grain growth. The fact that Gifkins measured a different activation energy for boundary migration during grain growth (7.5 kcal per mol) from that during creep (24.5 kcal per mol), although the specimens were of the same composition, shows clearly that such an effect exists under his experimental conditions; the presence of a simultaneous creep deformation markedly affects the boundary migration process in comparison with what would be observed under the same conditions but without the creep deformation. The failure of McLean&apos;s equation (Eq. [4] of Gifkins&apos; paper) to give a satisfactory dislocation density difference for boundary migration during creep is not surprising, since the activation energy which must be used in this equation refers only to the elementary atom transfer process of grain boundary migration. This activation energy value is approximately 6 kcal per mol for zone-refined lead, as determined in both the grain boundary migration experiments of Aust and Rutter31, 32 and the grain growth experiments of Bolling and Winegard.33 Using this activation energy value, McLean&apos;s equation gives reasonable agreement with observed migration rates for grain boundaries moving free of the influence of impurities.31, 32 The value of 24.5 kcal per mol is probably associated with the presence of impurity atoms, as Gifkins suggests. It should be noted, however, that this value was obtained using lead of only one composition and measurements at only two temperatures. The work of Aust and Rutter3"&apos; on the effects of tin, silver, and gold on grain boundary migration in zone-refined lead in the temperature range from 320" to 200°C, as well as the work of Bolling and Winegard34 on the effect of silver and gold on grain growth in zone-refined lead, shows that the measured activation energy is markedly dependent upon the kind and amount of solute present. Gifkins&apos; work does not permit evaluation of the effect of the 8 ppm of impurities other than oxygen present in his specimens. One incidental point: the symbols used to designate the experimental points of Fig. 6 appear to be in incorrect order in the figure caption. As the caption is printed, it would indicate that larger grain sizes were obtained after annealing at 47°C than at 100°C, which does not agree with the text (point M, p. 1019). Finally, it seems clear from Gifkins&apos; results that any serious attempt to determine whether grain boundary migration and grain boundary sliding during creep occur with the same activation energy, as Gifkins suggests and McLean rejects, must take into account the effects of impurities on these two processes, Although the work of Weinberg35 indicated that adding small amounts of copper, iron and silicon to aluminum did not affect the grain boundary shear behavior, it should be noted that his starting material contained approximately 60 ppm of impurities. Gifkins&apos; results indicate impurity effects at an impurity level of 8 ppm, suggesting strongly that the most significant impurity range to be investigated lies substantially below that value. R. C. Gifkins (author&apos;s reply) — As Drs. Aust and Rutter suggest, the results under discussion may have to be reinterpreted in the light of their own work on grain boundary migration, which was not available to me when the paper was written. Because of their work, Aust and Rutter attach more importance than I did to the activation energy for grain boundary migration during annealing (7.5 kcal per mol) obtained from a "direct" plot of log-rate against the reciprocal of absolute temperature. At the time it was obtained, this value seemed rather low, although it was similar to the value obtained by Bolling and Winegard.36 It was then, and still is, difficult to accept this value because of the low value of the index in the power law for grain growth, which seemed to indicate the influence of impurities. It was also concluded that the low value of the activation energy might have arisen from the manner of selecting rates of grain growth which were truly comparable at the two temperatures. There were many other indications in these experiments and those on recrystallization during creep3? that an impurity, probably oxygen, was of importance. The model for grain-boundary migration which Lucke and Detert had proposed was an obvious possibility and its use yielded an activation energy for boundary migration during annealing of 20 to 25 kcal per mol.

Jan 1, 1961

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice Chairman for Production of the Petroleurn Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive, locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert 2; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are deter-minable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations may be involved, our figures should represent as nearly as possible the total quantity of gas removed from the reservoir.

Jan 1, 1936

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice Chairman for Production of the Petroleurn Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive, locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert 2; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are deter-minable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations may be involved, our figures should represent as nearly as possible the total quantity of gas removed from the reservoir.

Jan 1, 1936

By R. A. Swalin, B. W. Roberts

ONSIDERABLE controversy has centered about the existence of an order-disorder transformation in alloys in the composition vicinity of 75 atomic pct Ni and 25 atomic pct Cr. All the evidence to date for such a transformation is of a rather indirect nature, since direct X-ray confirmation is difficult to obtain as a result of the small difference in X-ray scattering factors between nickel and chromium. As a result, superlattice lines would be very faint if present. Several investigators1-5 have observed anomalies in the electrical resistivity vs temperature curves of alloys in the vicinity of 25 atomic pct Cr. The observed change is characterized by a rather broad resistivity peak at about 540°C. A discontinuous drop in resistivity is normally associated with ordering. However, Taylor and Hin-ton4 have rationalized that the discrepancy could conceivably be caused by changes in the Brillouin zones upon ordering. The same investigators measured the specific heat as a function of temperature and have also observed anomalies in the vicinity of 540°C. Nordheim and Grant5 have proposed, because of the absence of superlattice lines and the absence of a discontinuity in the resistivity vs temperature curve, that long-range order is improbable and that the results could be better explained by short-range ordering. To date, however, the question has not been resolved satisfactorily. Neutron diffraction techniques provide a method for partially resolving the question since nickel and chromium have considerably different atomic scattering factors in the case of neutrons and, therefore, superlattice peaks, if ordering occurs, should be readily discernable. The results of a neutron diffraction investigation* coupled with a dilatometric in- vestigation are reported here. An alloy containing 28.0 atomic pct Cr was prepared from carbonyl nickel and electrolytic chromium in the form of a 1-in. diam x 10-in. ingot. Melting was done in an alumina crucible and casting in a graphite mold. The ingot was homogenized at 1250°C for seven days, after which a 5-in. long piece was cut into shavings in order to obtain a suitable neutron diffraction sample. Hardness samples and samples suitable for dilatometric analysis (% in. diam x 2 in.) were prepared from the remainlng piece. The neutron diffraction sample, along with a hardness sample, was annealed at 501°C for seven days, at which time the temperature was lowered to 479°C and held at this temperature for twenty-four more days. The hardness was observed to increase from 133 to 147 Vhn during the course of the annealing treatment, in qualitative agreement with Nordheim and Grant." Neutron diffraction traces taken at room temperature and at 42 °K are shown in Fig. 1. The insert shows the trace taken at room temperature with short counting times and thus only fair statistical accuracy. No evidence for superstructure reflections of Cu3Au-type ordering is observed. The statistical accuracy of the 4.2°K trace was improved by using longer counting periods. Several weak intensities are observed at small angles, including an aluminum reflection from the cryostat assembly and a very

Jan 1, 1958

By B. L. Averba

THE determination of retained austenite by X-ray diffraction uses the following relationship:"" Pa = constant . RVaA (8) [1] where: P is the diffracted power from phase a; R, the calculated intensity factor; A, the absorption correction; 8, the diffraction angle; and Va, the irradiated volume of phase a For a flat sample making a glancing angle + with the incident beam the absorption correction is calculated as: * 1 sin (28 - 4) A .= 1 [2] µ sin, (28 — 4) + sin 4 where µ is the linear absorption coefficient. Beu3 has proposed that the computed absorption correction be combined with the constant and that the experimental observation of the absorption correction used in the original method be eliminated. This procedure is permissible only if: 1—There is no preferred orientation in the sample, and 2—The geometric requirements have been met precisely. If these conditions are not met the validity of the determination is questionable. Unfortunately the necessary conditions must be tested experimentally for each determination, and this is done most easily by observing whether the apparent absorption has the form of Eq. 2. In practice it may be convenient to plot P/R vs the parameter sin (2? — )[sin (28 — +) + sin +] to obtain straight lines for the ap- parent absorption correction. Deviations from straight lines indicate either that the sample has not been positioned correctly or that the relative intensities are incorrect. Geiger counter spectrometer methods also have been used successfully for retained austenite determinations. In the usual spectrometer arrangement the sample makes equal angles with the incident and diffracted beams (8 = ); thus the absorption correction is simply 1/2µ and independent of 8. The retained austenite is then easily calculated from integrated intensity measurements on austenite and martensite lines. If the austenite content is not too low and if excessive fluorescence is not encountered it is possible to use filtered radiation and a recording spectrometer. The integrated intensities are then proportional to the areas of the diffraction peaks. For lower austenite contents the following technique was used: A bent quartz monochromator and a Geiger counter spectrometer are employed. The monochromatic radiation is focused on the front slit, and the counter slit is made broad enough to include the entire line. A series of readings are taken in the vicinity of the diffraction peak. The highest reading includes the diffraction line plus background. The background is obtained from the average of several readings on each side of the peak. The integrated intensity is obtained by subtraction. CrK, and FeKa have been used for such determinations. This technique has been found to be as sensitive and as accurate as the photographic methods. In the spectrometer methods the ratio austenite/ martensite may be obtained from readings on austenite and martensite lines and the application of Eq. 1. It is also possible to use external standards and to obtain the austenite contents from measurements on the austenite lines alone. The small correction for carbides then becomes unnecessary. The best standards are probably samples with known

Jan 1, 1954

By J. H. Frye, J. L. Scott, J. W. Woods

THERE are at least two effects of temperature on the stress required to produce plastic flow. 1) Metals plastically strained for the same amount at different temperatures possess different stress-strain curves and different internal structures (e.g., nature and density of imperfections). 2) There is both experimental and theoretical evidence that the stress necessary to produce plastic flow may vary with temperature even though the internal structure remains constant.1-5 Much of the data in the literature is difficult to interpret because these two effects are simultaneously present. In the work reported here, they are considered separately. Standard 0.505 in. tensile specimens were prepared from high-purity Mond nickel and OFHC copper. Nickel specimens were annealed in hydrogen at 1150°C for 30 min and furnace cooled. This produced an average grain diameter of 1.4 mm. Copper specimens were annealed in vacuum at 525°C for 6 hr and furnace cooled. This produced an average grain diameter of 0.11 mm. Nickel tensile specimens were prestrained in tension at 500°K, whereas copper tensile specimens were prestrained in tension at room temperature. All specimens were cooled to 74°K and heated to room temperature. After these treatments all of the tensile specimens of a given set possessed identical structures. All specimens were returned to the tensile machine and tested at various temperatures and constant cross-head speed. Many of the tensile curves showed well defined yields but, in order to minimize personal judgment, the yield was always chosen as the stress corresponding to 0.2 pct plastic deformation. Results are summarized in the graph of yield vs temperature of test, Fig. 1. All of the specimens corresponding to any one line have had identical treatments and, therefore, have identical internal structures. Thus, each line gives the relation between yield stress and temperature for one constant internal structure. The lowest line, which is for annealed nickel, shows no measurable variation of yield with temperature. This is similar to Blewitt&apos;s6 results on copper single crystals, but a variation in yield with temperature was found by Andrade and Henderson&apos; in single crystals of nickel, and by Car-recker and Hibbard8 in annealed polycrystalline copper. The three other lines, which are for prestrained materials, show that there is a linear relation between yield stress and temperature when the internal structure remains constant. Such a relation might be expected from a rate equation such as that of Kauzmannl on the assump- tion that the activation energy is either independent of or linear with temperature. These results would also be expected if the shear moduli of copper and nickel are linear functions of temperature for, as Cottrell and Stokes have pointed out," in all dislocation theories of strength the flow stress appears proportional to the shear modulus of the material. In copper and nickel, since the modulus of elasticity decreases roughly linearly with increase in temperature," it is probable that the modulus of shear also decreases approximately linearly with increasing temperature. A detailed discussion of the effect of these and other factors on the temperature dependence of flow stress in face-centered-cubic metals has recently been given by Seeger.4

Jan 1, 1958

By J. P. Hammond, C. J. McHargue

THERE have been no publications on the wire texture, on the cold-rolled sheet texture, nor on the recrystallized sheet texture of vanadium. Since it has a body-centered cubic structure, it would be expected to show strongly preferred orientations such as are found in iron&apos; and molybdenum.&apos; The wire textures of body-centered cubic iron,3 tungsten," molybdenum,5 antalum,6 iobium,6 and brass6 have been found to have [110] directions lying parallel to the wire axis. Wires of iron,&apos; containing 1.95 pct V or 1.95 pct Si,7 and steel8 retain their texture upon recrystallization. Molybdenum9 and tungsttln&apos; wires retain their texture after recrystallization at low temperatures. A [loo] recrystallization texture has been reported for mo1ybdenum9 and for a Fe-Ni alloy (53 atomic pct Ni).10 The cold-rolled sheet texture for iron,&apos; mild steel," and molybdenum chiefly one in which the [110] directions lie parallel to the rolling direction and the (100) planes lie parallel to the rolling plane with a deviation from this position chiefly about the rolling direction as an axis. This paper presents the cold-rolled and the re-crystallized wire textures, and the cold-rolled and the recrystallized sheet textures for vanadium. The results show that the textures in vanadium are not significantly different from those reported for other body-centered cubic metals. The vanadium used in this investigation was the so-called "ductile" vanadium which has a nominal composition within the following limits:12 0, 0.05 to 0.12 pct; H, 0.001 to 0.004; N, 0.02 to 0.04; C, 0.03 to 0.07; and V, 99.8 to 99.9. The wires were formed by rolling annealed rods of 0.280 in. diam to 0.028 in., a reduction in diameter of 90 pct. The wires were then electrolytically etched to 0.005 in. diam and used as such for specimens. Annealed sheet was reduced 95 pct in thickness from 0.100 to 0.005 in. with a two-high, 4-in. diam mill using reductions no greater than 10 pct per pass. In order to avoid temperature effects, the sheet was allowed to cool between passes. X-ray specimens were made in the form of posts from the sheet. The sheet was mounted in a fixture and the edges were polished using metallographic technique. Each edge was alternately polished and etched during the last stages in order that all worked material would be removed. These post specimens were approximately square in cross-section. The specimens to be recrystallized were wrapped in tantalum foil, sealed in evacuated quartz tubes, and annealed at 1600°F. The X-ray data were obtained from transmission shots made with a 0.030 in. pinhole camera, and molybdenum radiation with a zirconium filter inserted between the specimen and film. The grain size was sufficiently small in both the cold-worked and recrystallized material to give satisfactory results with the specimens stationary. In order for the wire texture to be determined, transmission X-ray patterns were taken with the

Jan 1, 1953

By E. H. Edwards, J. Washburn

Zinc crystals were deformed in simple shear and it was found that anisotropic strain hardening occurred in which the inactive slip systems were hardened more than the active system. The formation of dislocation barriers by dislocation interaction was discussed as a possible explanation of the hardening of the latent systems. STRAIN hardening which accompanies slip in a metal crystal is not limited to the slip systems actively contributing to the plastic strain. There is also a strengthening of the latent slip systems which are crystallographically equivalent to the active system. In the case of aluminum deformed in tension, Taylor and Elam1 found that plastic flow on one set of octahedral planes caused either the same or a slightly greater hardening on an inactive set. Similar results have been obtained for crystals of a brass2 and of Cu-A1 solid solutions.3 Experiments by Rohm and Kochendorfer4 indicated that the hardening of the active system exceeded the hardening of any latent system for aluminum crystals deformed in shear. On the other hand, strain hardening in zinc and cadmium crystals tested in simple shear at —196°C was recently found to be greater in the latent than in the active slip direction." When the strain direction was shifted during testing to a direction 60" from the original, a higher stress was required for glide to continue than would have been needed for flow to proceed in the original direction. The relation between the hardening of active and latent systems must be complex, depending upon the relative orientations of the systems and upon the experimental techniques used to deform the crystal. A detailed knowledge of the hardening produced in latent systems would be valuable in choosing between possible dislocation models of the strain-hardening process. The experimental data now available are incomplete and even contradictory. The present study was undertaken to provide quantitative information regarding the relative amount of hardening of active and latent systems for a particularly simple case. Zinc crystals were deformed in simple shear along one of the three crystallographically equivalent directions [250], [1210], and [1120] in the slip plane, and the relative hardening produced in each of these directions was compared. Experimental Procedure and Results The single crystals of 99.99 pct purity zinc used in this investigation were grown from the melt in the form of 1 in. diam spheres. Shear specimens were acid-machined from the crystals by a method which has been described previously. The gage section of the test specimen was a cylinder having a height of 1/8 in. and a cross-sectional area of approximately 1/3 sq in. All specimens were machined with the axis of this cylindrical gage section aligned with the [0001] axis of the crystal. An innovation in the design of the shearing apparatus for these tests was the provision for a rapid shift in the direction of the applied stress from one slip direction to any other slip direction lying in the same slip plane. Fig. 1 shows a section through the specimen and shearing apparatus, and Fig. 2 is a

Jan 1, 1955

By J. B. Newkirk

Results of a Debye-Scherrer X-ray investigation are given which show that the order-disorder transformation is a first-order or heterogeneous reaction in Cu-AU alloys with compositions near CuAu. Evidence was found for conventional tie-line segregation across a usual type of two-phase field separating the ordered and disordered fields in the Cu-Au equilibrium phase diagram. The horizontal and vertical widths of the two-phase fields are about 3 atomic pct and 20°C, respectively, at 43 and 54 atomic pct Au. No evidence for the existence of an ordered structure based on a stoichiometric composition of Cu3Au2 could be found. ALTHOUGH the modern theories relating the de-Agree of order of binary alloys to temperature and composition have met with considerable success, the nature of the transformation from the disordered state to the ordered state and vice versa has never been well understood. It has been assumed by some&apos; that this is a second-order transformation, that is, a homogeneous change of state. Others2 hold that the transformation is first-order and that the effects characteristic of heterogeneous phase transformation apply. Since this subject is discussed in detail in a recent paper,&apos; the arguments will not be repeated here. The present paper summarizes an experiment which was designed to distinguish between these two viewpoints for the case of Cu-Au alloys near the composition CuAu. The Cu-Au system is an important one because it furnishes prototype alloys, the behavior of which has formed the basis of much of the present-day order-disorder theory. It has recently been shown- hat in alloys near Cu3Au there is a temperature range within which the ordered and disordered states coexist in equilibrium and are distinguishable as separate phases. Therefore, the transformation must be first-order for these alloys. A similar demonstration for alloys near CuAu, however, has been lacking. Experimental Method Essentially the experiment consisted of equilibrating Cu-Au samples at various temperatures, quenching them in water to retain the high temperature states, and then examining them at room temperature for the coexistence of the ordered and disordered structures. The thermal gradient method of heat treatment- as used because it was important that all temperatures over the transformation range should be represented in the test. Briefly, this method consisted of holding a wire of the desired composition, sealed under vacuum in Pyrex, in a known temperature gradient for a long enough time to allow each part of the wire to assume the crystal structure characteristic of the temperature at which it was held. The temperature gradient was produced by inserting into an ordinary wire-wound cylindrical laboratory furnace, an 18 in. length of 1/8 in. ID ceramic tube which was heavily wrapped with asbestos. The furnace power was controlled by a Tag-liabue Celectray controller and a chromel-alumel thermocouple with the junction located on the heating elements. During the equilibrating treatment the widest variation of temperature within the gradient tube was approximately 4°C at the highest temperature. The temperature at various places within the tube was determined, before inserting

Jan 1, 1954

By J. L. Meijering

Oxidation hardening of cylindrical and spherical specimens first decreases with depth below the surface, but then increases again as the center is approached. This is in agreement with the view that this change in hardness is mainly determined by the change in velocity of the oxidation boundary, which affects the dispersion of the oxide. WHEN a thick slab of silver containing 0.3 pct Mg by weight is internally oxidized, the hardness measured on a cross section is found to decrease considerably with distance from the surface.&apos; This phenomenon has been attributed to the diminution of the velocity of the oxidation boundary. The smaller this velocity is, the more slowly the free-oxygen concentration rises towards the concentration in equilibrium with the oxygen gas. And a small 0 concentration favors dissociation and thus conglomeration of the oxide. For instance, the hardness decreases more rapidly during long annealings in nitrogen than in air.&apos; Measurements by Gregory and Smith3 on sections through internally oxidized Al-silver wire showed a smaller variation in hardness, probably because the wire diameter was only 0.9 mm. Wood4 found a drop in hardness with depth in internally oxidized Al-copper strip, and also—by electron microscopy—the concomitant increase in Al2O3 particle size. Under certain circumstances internal oxidation leads to formation of rather irregular inner oxide films in the midst of dispersed oxide. This special sort of conglomeration—discussed in Ref. 5—is also favored by greater depth below the surface.3,5 In this paper hardness measurements in large diameter cylindrical and spherical specimens are described. Here the oxidation velocity* goes through ness initially decreases with depth but increases again towards the center. Normally, the diffusion coefficient D1 of oxygen is very large compared to D2, that of the dissolved metal. If, furthermore, the atomic fraction c2 of the latter is much larger than the O-solubility cl- but c2D2 << c1D1- the velocities in question are easily calculated2 to be: for the cylinder and for the sphere. Here p is the radial coordinate of the oxidation boundary and R the specimen radius, which in dilute silver alloys is constant, as no external oxidation occurs. These equations have been derived for a divalent solute; for nondivalent solutes c2 has to be multiplied by half the valency. The equations are not valid near the center. For which can be considered as a standard case,2 the Eqs [I] and [2] begin to yield U-values which are appreciably too high for p/R = 0.05 and 0.15, respectively. But at the v-minima they are still very good approximations. These minima lie at p = emlR= 0.37R in the cylinder and p = 1/2 R in the sphere. Other factors besides the velocity v will also influence the hardness. The oxide concentration cox is constant in a flat strip, apart from a narrow region in the middle,2 but in cylindrical and spherical specimens cox decreases steadily with depth. When C1 << c2 and c1D1 >> c2D2 one can calculate

Jan 1, 1961

By R. P. Thomas

Secondary fertilizer minerals are the mineral materials used to supply directly and indirectly the secondary and trace plant food nutrient needs of a fertilizer. Since few soils contain sufficient availability of all plant nutrients for their proper growth, man has prepared mixtures of plant food materials to correct these nutrient deficiencies. These mixtures or fertilizers, when added correctly to a soil, make it possible for abundant and economic crop growth. Many kinds of materials are used as sources of these needed nutrients. They come from natural and synthetic materials and minerals including many beneficiated byproduct compounds. A fertilizer consists largely of carriers of one or more of the three major plant foods, namely nitrogen (N), phosphorus-phosphorus pentoxide (P2O5) and potassium-potash (K2O). Many other nutrients are just as essential for plant growth as the three major plant foods. In fact, the efficient use of fertilizers today depends upon an adequate supply of all these other nutrients. Since these additional materials are usually removed from the soil by plants and supplied in fertilizer in less quantities than the major nutrients, they are called secondary and minor nutrients. In the early days these special nutrients were contained as impurities in the primary nutrient carriers. Today, fertilizers are made primarily from concentrated and synthetic materials which carry very few of these other essential nutrients. Consequently, many secondary and trace nutrient carriers, as salts, byproduct compounds and even minerals have to be added to fertilizers. Secondary Nutrient Carriers The secondary plant foods in fertilizer are next to the major nutrients in abundance. They are calcium, magnesium, sulfur, chlorine, silicon and sodium. Although many of these elements are added to a fertilizer as part of the major nutrient carriers, they are also added in special carriers. The large tonnage of these secondary nutrient carriers used in fertilizers represents only a small percentage of the total production of these materials. A fertilizer producer thinks in terms of materials which supply nutrients instead of minerals. Therefore, these materials will be discussed by elements. CALCIUM Soils need calcium to supply the nutrient needs of plants and maintain the desired physical and biological conditions in the soil. The available calcium is usually 40 to 80 pct of the exchangeable bases. (These bases are ones which can be displaced by other cations and determined quantitatively. They are then expressed as milliequivalents per hundred grams of soil-me.) Direct applications of lime materials such as burnt, ground or hydrated limes are the important sources of calcium for the soil. Most crops, especially legumes, have a high requirement for calcium. The average farmer does not use enough lime to maintain the proper level of available calcium. Hence, it is necessary for many fertilizers to contain soluble calcium materials for efficient use of the major nutrients. The following major nutrient carriers supply some calcium: calcium nitrate, ammonium nitrate mixtures and cyanamid, and many of the phosphates. Both synthetic and natural gypsum are used in fertilizer production. Some crops such as peanuts require a large amount of soluble calcium. Gypsum is the important supplier of this soluble calcium. It is not applied with the fertilizer

Jan 1, 1960

By F. W. Glaser, W. Ivanick

A pressure-sintering method was used to produce binder-free and very dense TiC specimens. Some physical properties of these TIC bodies were determined and found to compare favorably with those of certain cemented Tic grades. It was also observed that the hot transverse rupture strength of TiC bodies remained substantially the same regardless of the amount or type of binder material used. STUDIES of the structure and physical properties of refractory materials have been intensified recently because of the urgent need for nonstrategic materials that retain their strength at high temperatures. Research aimed at determining and improving the physical properties of cemented carbides and borides has been accelerated with a view toward possible use of such materials in connection with turbine blades, rocket nozzles, and other high temperature applications. On the hypothesis that the strength requirements in connection with some of the above applications could be met only by proper choice of cementing agents for such refractory materials, the literature describing the physical properties of borides or carbides was reviewed. However, with a few exceptions,&apos;-" references were found only to compositions containing at least one or more auxiliary binder metals. Cobalt and nickel are among the most frequently employed cementing agents. The melting point of Tic (approximately 3250°C) and therefore the sintering temperature, at which notable densification of a cold pressed Tic powder compact could be expected in the absence of a liquid binder phase, is relatively high. The present study makes use of a high temperature, pressure-sintering procedure, recently described by one of the authors in connection with the sintering of binder-free ZrB,," to produce dense bodies of sintered Tic—free of any cementing agent. During the course of this sintering study, some physical properties of dense Tic bodies produced by this method will be discussed. Materials, Preparation of Samples, Testing Methods The procedure for the forming of Tic powder consisted of mixing graphite and TiH, powders in stoi-chiometric proportions, and heating this mixture in a H, atmosphere and carbon crucible by high frequency, to temperatures ranging between 1900° and 2100°C (3452" and 3812°F). The powdered carbide was then comminuted and screened to the desired particle size. Table I shows the chemical analysis of the two grades that were employed for the production of samples during this work. Bodies of Tic, approximately 2.5xlx0.5 cm were produced in graphite molds that were heated by direct conduction. Sintering was carried out at temperatures for time intervals ranging from approximately 0 to 30 sec under a constant pressure of about 1.3 tons per sq in. An alternate method for the production of samples consisted in cold pressing the individual Tic grades at pressures ranging from 4 to 10 tons per sq in. and sintering in a hydrogen atmosphere in graphite crucibles heated by high frequency induction. Sintering temperatures ranged from 2600° to 2900°C (4715° to 5255°F). Electrical testing was done by measuring potentiometrically the voltage drop over a length of 1.5 cm for a current of 10 amp at room temperature. Cross-sectional areas as well as densi-

Jan 1, 1953

By J. R. Johanson

With the continuing development of automatic operations, it is important that reliable discharge rates through hoppers and bins be obtained for bulk solids. In most applications a feeder is used to control the feed rate. The selection of this feeder size is usually based on the rated ability of the feeder to move material without regard to the capability of the material to flow through the opening in the hopper onto the feeder. The dis charge rate through a given hopper opening may vary from zero to a theoretical maximum depending on the flow properties of the material. This paper presents an equation for the maximum discharge rate for a bulk material as a function of the hopper shape, the opening size and the flow properties of the material. Discharge-rate tests on various materials indicate good agreement with calculated values for opening sizes from a fraction of an inch to several feet. As part of a program to develop improved design criteria for bulk storage and handling facilities, a specific study of the methods involved in calculating the rate of discharge of bulk solids from hoppers and bins has been made. This study is closely related to earlier work done on the prevention of flow problems through the choice of proper design geometry of hoppers and bins1. The present paper is an extension of this earlier work, and therefore many of the concepts previously derived and explained will be used without explanation. Two types of flow will be considered: plane-strain flow in a wedge-shaped hopper and axial-symmetry flow in a conical hopper. The literature contains many studies on discharge rate for regular-shaped dry particles2*3 such as glass beads, lead shot and coarse dry sand. However, the work is empirical in nature, and it is difficult to extrapolate the given information to apply to moist, sticky materials typical of many industries. Some studies4 have shown a decrease in discharge rate with an increased moisture content of the material. However, no attempt was made to correlate the discharge rate with moisture. The method of calculating discharge rate presented in this paper was derived analytically from the basic knowledge of the flow of frictional, cohesive, granular solids, The equation includes the effect of material cohesion (stickiness), hopper configuration, opening size and bulk density of the material. THEORETICAL WORK The basic assumptions made in deriving the discharge rate equation are as follows: 1) The material is a frictional, cohesive, granular solid. 2) The flow is considered continuous and without significant density change. 3) The material at the hopper opening forms a continuously failing arch that is in dynamic equilibrium. 4) The strength of the material in the arch, which must be overcome for the arch to fail, is caused by the pressure in the flowing mass near the hopper opening. 5) This pressure at the hopper opening can be calculated5. If we consider the dynamic equilibrium of an arch of uniform thickness such as that shown in Fig. 1,

Jan 1, 1965

By Nicholas J. Grant, Bill C. Giessen

The phase diagram Ta-Ni has been treated repeatedly; investigations up to 1958 are summed up in Ref. 1. Since then, an equilibrium diagram has been presented by Kornilov and Pylaeva.2 They found the following intermediate phases: Ta2N; (CuA12 type),3 "TaNi" (p phase, Mo8Co7 type), TaNiz, and TaNi3 (Ticus type).5 Of these, the crystal structure of TaNin remained unknown, and no further literature reference was found. According to Kornilov and pylaeva,&apos; TaNil melts peri-tectically at 1420°C. A 5-g alloy of Ta + 66.7 at. pct Ni was prepared by inert-gas arc melting using 99.95 pct Ta rod (NRC-MG) and 99.9 pct Ni shot (Fisher). The weight loss after three melts was <2 mg; a microscopically homogeneous ingot resulted. As shown in Ref. 6, no oxygen or impurity pickup needed to be considered under these conditions. Specimens were annealed for 15 hr at 1350°C, 15 hr at 1205oC, and 15 hr at 875°C with subsequent powdering and stress relief for 10 min at 1350°C, 15 min at 1205oC, and 1 hr at 875oC, respectively. Micrographs and X-ray analysis (114.6 mm Norelco camera, filtered CuK, radiation) showed homogeneous one-phase alloys in the as-cast state and at all three temperatures, all having the same powder pattern except for broad lines in the as-cast state. From this it is concluded that either TaNi, melts congruently or its melting behavior is a transition between the eutectic and peritectic cases. Since it was found that very slight surface contamination on stress relieving can considerably alter the structure of similar phases (e.g.,TaPt3),7 patterns before and after stress relief were also compared; they were identical except for line broadening in the non-stressrelieved condition, and two faint impurity lines in the stress-relieved samples. The powder pattern is presented in Table I. All lines were accounted for by indexing with a tetragonal lattice, 0Yh- I4/mmm , with a, = 3.154 ± 0.001A, co = 7.905 * 0.002i and c/a = 2.506. The atomic positions are: 1000; 1/2, 1/2, 1/2] + 2Ta(a): 000; + 4Ni(e): *(002); z = 0.333 * 0.002 This proves TaNi2 to be a representative of the MoSiz (Cllb) type. The variable parameter was determined by grouping the visually estimated intensi- ties according to their 2 indices, plotting their F values, and varying z for best fit, which was obtained at z = 0.333= 1/3. Since absorption was not considered, only the relative intensities with similar 28 can be expected to agree. The interatomic distances are presented in Table 11; the standard error is *o.o2A, resulting chiefly from the uncertainty in z. These distances indicate a coordination number 10 for both kinds of atoms and show that the pseudohexagonal layers along (110) are rather un-distorted. The mean atomic volume of 13.1A3 is close to the Vegard&apos;s law value of 13.3A3, showing

Jan 1, 1964