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By H. H. Stout

In the early fall of 1925, the writer was conducting, in the Ledoux and Co. laboratory, New York, experiments directed toward ascertaining the effect on its impurity content when cathode copper was subjected to a current of various gases at an elevated temperature below the melting point. The apparatus consisted of a vertical I-in. dia. silica tube about 12 in. long, heated on the outside. The cathodes were broken to pass 3/8-in. mesh, and a current of various different gases was passed up through a 4-in. long column of these loose cathode particles in the vertical tube furnace. Temperature was maintained to 1500º to 1600ºF. and the gas treatments lasted from 3 to 6 hr. The writer observed that whenever reducing gas (H2 or CO) was used, these cathode particles stuck together at points of contact with each other. The cohesion was so marked and tenacious that an examination was made of the fractured surfaces, when cathode particles were broken from the cluster. Crystal growth was always found to have taken place across the surfaces where separate particles were in contact, but only after all oxides, sulphates, etc., had been completely removed. The idea of a possible new process was then conceived and was disclosed to A. M. Smoot (V. P. Ledoux and Co.) with intent to obtain his views. The first conception as given Smoot was "to gas-clean broken cathodes, put them in an extrusion press, solidify and extrude them at around 1500ºF." Smoot's reaction, after a few moments considera- tion, was, "It looks perfectly all right to me.'' The writer and his assistants, W. H. Osborn and H. H. Stout, Jr., after conferring as to ways and means, decided to go ahead with preliminary laboratory experiments, which, it was thought, would move the new process from the possible to the probable. This program followed a course indicated by three basic considerations: 1. Since brittle cathodes were often unintentionally produced, it seemed probable that the laws controlling this type of deposition could be ascertained. 2. We had already proved the gas-cleaning feature. 3. There remained to prove: whether a sound, homogeneous metal billet could be produced with crystal growth established over the entire surface of each individual particle in the billet; and, if so, what would be the physical properties? Osborn arranged with Columbia University for conducting experiments in its research laboratory to prove or disprove the third item; Columbia assigned C. A. Phillipi, Jr. to assist in the project. A press with a cylinder 2 in. high and of I-in. dia. was used. It was surrouilded and heated by a resistance coil 01 Nichrome wire. Broken tough cathodes were used. Experimental Procedure The first run took place March 18, 1926. The resistance wire gave out when temperature of 1000ºF. was obtained. Pressure was immediately applied: perceptible ram movement stopped when 39,000 lb. per sq. in. on the copper was reached, with a maxi-

Jan 1, 1941

By John Chipman, Helen Towers

DEVELOPMENT of a simple radioactive tracer technique for measurement of the diffusion coefficient of calcium ion in liquid slag has already been reported. The investigation was of a preliminary nature designed to explore the possibilities of using radioactive isotopes and to establish a method, and no great accuracy was claimed for the results. It was shown, however, that Ca15 could be used successfully, and the values obtained for the diffusion coefficient appeared to be of the right order of magnitude. However, it was considered that a better technique could be devised for carrying out the diffusion. The experiments were, therefore, continued to find a more accurate method, to check the calcium results, and to extend the investigation to include measurements of the diffusion coefficient of silicon in the same slag. There were two flaws in the original technique. Convection was the cause of too many failures, and the interface between the two slags in the diffusion cell was curved rather than plane, probably due to a surface tension effect caused by the addition of the tracer Ca45 in the form of chloride. Two methods of overcoming these defects were tried. Since it was planned to study diffusion of the short-lived isotope Si"' also, the development of methods was restricted to those which gave promise of being reasonably rapid. Method 1—The principle was identical to that previously used with respect to the diffusion conditions, but there were three differences in technique. Temperature control was more rigid, the tracer was added to the slag as Ca45O rather than the chloride and, finally, an effort was made to translate to high temperatures the elegant method developed by Cohen and BruinV or bringing together the two liquid layers and beginning the diffusion. A master slag was melted in graphite, ground to a fine powder, and analyzed (38.5 pct Ca0-20.9 pct Al2O3-40.5 pct SiO2). The tracer was received as Ca45C12 in an aqueous solution of CaC12 + HC1. From this, calcium oxalate was precipitated, ignited to calcium oxide, and added as such to the slag to give an activity of approximately 5 µc per g. The mixture was then melted into the form of a cylinder 3/16 in. diam and about 1 in. long. A solution identical to the tracer solution without Ca45 was given exactly the same treatment. The resulting Ca40O was mixed with that slag which was to form the tracer-free half of the diffusion cell, and this was likewise melted into a cylinder of the same size. Slag cylinders, two with and two without Ca15, were set in graphite blocks as shown in Fig. 1, and the crucible was lowered into position in the fur-

Jan 1, 1958

By Irwin Roman

In studying the possibilities of a continuously recording magnetometer for use along the surface of the earth and in an airplane, the Federal Bureau of Mines was led to a study of the theoretical resolving power of magnetic observations, both in the variation of the total magnetic intensity and in each of the two cornponents ordinarily measured. Along with this general study, an attempt was made to determine the relative worth of the total intensity anomaly and the vertical anomaly in geophysical prospecting. Genera1 considerations led to three conclusions: I. In the northern magnetic hemisphere of the earth, the total intensity anomaly is offset to the south of the vertical anomaly, for a positive anomaly (see Appendix, note 1). 2. The resolving power of magnetic observations decreases rapidly with distance from the disturbing body. 3. The horizontal anomaly has little value in prediction of the disturbing body but might be useful in making a choice between bodies suggested by the vertical or total anomaly. Some of the considerations leading to these conclusions were: I. The normal intensity and the anomalous intensity are vectorially additive; hence for a positive anomaly in the northern magnetic hemisphere the total intensity will be a maximum at some point south of the disturbing body and north of the point at which the line to the disturbing body is parallel to the normal earth's field. The anomaly itself has a maximum value directly above the body. For a positive anomaly of constant magnitude, the total intensity will be a maximum when the anomaly vector is parallel to the normal vector. This is shown schematically in Fig. I (not to scale) for a magnetic distribution not restricted to a relatively thin sheet in the magnetic meridian. The normal field has a magnitude 10 with vertical component V0 and horizontal component Ho. Six station points along a traverse across the body from south to north are shown at M to S. At each of these stations the normal magnetic field vector terminates at F. At each of these stations the magnetic field vector due to the disturbing body B terminates at A. The line through the station point and the point A passes through B. The magnitude of the anomaly, indicated by the length of the vector terminating at A, is proportional to some power of the distance from the station point to the disturbing body. If the disturbing body B is a concentrated point of magnetic material, the anomaly is proportional to the inverse second power of the distance. For a uniform magnetic distribution over a line perpendicular to the observed traverse, the anomaly is proportional to the inverse first power of the distance. For surface distributions, the law of intensity is more complicated. At each field point, the total magnetic intensity T is the vector sum of the

Jan 1, 1949

By L. G. Schulz, P. Spiegler

The electrical resistivity and the temperature coefficient of resistivity were measured with a potentiometric method using pure mercury as a reference material. Measurements were made nea,v roorn temperature. A detailed study was made of Hg,TI, near its melting temperature. THE work to be described was originally undertaken to provide the necessary data for interpreting the results of some optical experiments,' but because of the growing importance of liquid metals,273 it appeared that the results of the resistivity measurements should be published separately. For convenience the alloys selected were those which are liquid at room temperature. Special consideration was given to the Hg-T1 alloy closely corresponding to Hg,Tl, because recent X-ray diffraction results of Smallman and Frost seemed to show that the solid structure may persist to some extent into the 1iquid. EXPERIMENTAL PROCEDURE A potentiometric method was employed in which the resistivity of mercury was used as a reference. The essential features of the samples are shown in Fig. 1. A capillary tube CT with a bore of approximately 1.5 mm was fitted into two end cups, T, which were made of Teflon. A pair of current electrodes CE were immersed into the excess liquid metal which partly filled the end cups. The potential electrodes PE were inserted into CT through short pieces N of a no. 18 hypodermic needle held in place with Saureisen cement SC. As shown, the lower ends of the PE7s were reduced in diameter to 0.25 mm to minimize the distortion of the liquid metal cross section. Several methods were used to insert an alloy into the sample, but the usual one with mercury alloys was to fill the sample container with a weighed quantity of pure mercury* and then add weighed the sample tube in a vacuum. Because of rapid corrosion, samples containing gallium were of necessity prepared in a vacuum. To obtain the specific resistivity of an alloy the resistance of the sample containing the alloy was measured and compared with the resistance when the container was filled with mercury. Resistances were measured in the temperature range of 20" to 60°C to obtain the temperature coefficient of resistance. The electrical measurements were made by connecting the sample in series with the standard one-ohm resistance, and the potential drop measured alternately over the sample and the standard resistance. To correct for stray thermoelectric effects provision was made for reversing the direction of the current, and the true potential drop was taken to be the average of that obtained for the two directions of current flow. Various materials were used for the electrodes, the most uniform results being obtained with nickel. EXPERIMENTAL RESULTS The numerical results are presented graphically in Figs. 2 and 3 and in tabular form in Tables I and 11. Following are remarks on results of individual alloys. 1) Hg-In—This was the first alloy studied, and

Jan 1, 1960

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By L. S. Darken

It has been known for sometime that in an ionic lattice, such as that of Ag,S or FeO, the migration velocity of the anion may differ markedly from that of the cation, the cation being usually the more mobile. It has been shown, for example, that during the formation of silver sulphide tarnish on silver, the tarnish layer grows principally by the motion of silver cations through an essentially stationary silver sulphide lattice. Similarly, the growth of wüstite scale on iron proceeds principally by motion of iron ions, this being accomplished with the aid of vacant iron lattice sites into which the iron may readily move. Likewise investigations of solid solutions of various salts show that there is usually considerable difference in the mobility of the different cations. Measurements of the mobility of various metals in liquid mercury indicate that the various metals move at different rates relative to the mercury. In view of the foregoing it seems reasonable to suppose that when any single phase solution is acted upon by a field, the atoms of different elements respond in different ways; in particular, that the force arising from a particular concentration gradient in a binary alloy would cause the atoms of one component to move with a drift velocity which is in general different from that of the atoms of the other component. The recent experiments of Smigelskas and Kirkendall' support this viewpoint, since they found, in essence, that during diffusion in alpha brass zinc moves appreciably faster than copper. This was evidenced by the relative motion of inert molybdenum wires. Such a phenomenon is incompatible with the place interchange theory of diffdsion proposed by several authors, most recently by Bir-chenall and Mehl.2 This theory has, however, also been questioned3v4 for other reasons, principally because of the high energy required for direct atomic interchange. The rather large difference between self-diffusivity, as determined by tracer technique, and mutual diffusivity, as determined with the aid of another element at low concentration, might also be interpreted as favoring the above idea; however. Birchenall and Mehl have pointed out that there is another possible interpretation of this difference; this is discussed later. A rather interesting and pertinent observation was made by Schwartz, who noticed that tungsten lamp filaments, heated by direct current, commonly fail by necking down in the region at the temperature gradient near the positive end, with a concomitant swelling at the corresponding position near the negative end. He introduces considerable auxiliary evidence to show that this phenomenon is occasioned by the motion of tungsten cations which migrate in the high temperature region from the positive end toward the negative end. The mechanism of this migration is not clearly understood. If, however, this experimental evidence be accepted, we are forced to conclude that alloying elements in the tungsten may migrate by the same or a Similar mechanism, whatever it may be, at a greater Or lesser rate, thus giving rise

Jan 1, 1949

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By K. L. Moazed, G. M. Pound

An investigation was made of the deposition of silver from a thermal beam onto tungsten field-emitter tips at 300°K. "Island"-type nuclei were observed to form and grow. The nucleation of silver crystals occurs preferentially on non-close -packed planes of a tungsten tip at a critical volume free-energy change of about —2900 cal per cc. The adatom population which is critical for appreciable nucleation rate of silver crystals is about 0.2 of a monolayer and is essentially independent of beam flux, time, and source temperature. This result is strong evidence that a metastable equilibrium exists between adatoms and critical nuclei, as assumed in the present theory. SOME of the more significant studies of nucleation in deposition of metals from vapor beams have been conducted by measuring the thermal beam flux which is critical for appreciable rate of nucleation on a substrate surface held at a given temperature.'2 The observed critical supersaturations may be described in terms of Eq. [7] which was derived3'3a on the model of an adsorption, surface migration, and statistical fluctuation mechanism. However there usually made with a low-power optical microscope, a fairly insensitive method of detection. The object of the present study was to overcome some of these difficulties by measuring the critical supersaturation for condensation of a thermal beam of silver onto a tungsten field-emitter tip. Such a tip may be cleaned by electrically heating it to a high temperature in situ, and the high vacuum obtainable in a field-emission tube (10-10 torr) precludes adsorption of residual gases for convenient periods of time. Furthermore, the degree of cleanliness, the orientation, and the state of imperfection of the tip may be ascertained from the field-emission pattern. Detailed explanations of theoretical considerations and experimental procedures relating to the field-emission microscope may be found in a number of excellent review articles12'13 and thus only a brief description will be given here. The electronic work function of a metal is defined as the energy that an electron needs to escape from the potential field of the solid. By applying a large field between the surface of the solid and a suitable collector, it is possible to free the electrons by the tunnel effect. Fields of approximately 30 million v per cm are needed to produce this effect, and such fields are obtained in practice by using microscopic surfaces of high curvature (tips). Because the work function of a metal is a function of surface orientation, the emission from the various planes is different, and thus it is possible to obtain a representation of the surface in the emission microscope. In general, the work function is higher for the more densely packed planes. Fig. 1 shows a pattern for "clean" tungsten in which the central dark region represents the (110)

Jan 1, 1964

By N. J. Grant, Hans Brunner

ThE materials used in this investigation were furnished by the Aluminum Co. of America and consisted of high-purity alurhinum (99.995 pct) and two aluminum-magnesium alloys containing approximately 2 and 5 pct Mg. The compositions of these alloys are listed in Table I. The materials were received as hot rolled 3/8-in. diam rods and were made from the same heats as the materials which were previously used in this laboratory.'j3 The rods were cold swaged to 1/4-in. diam by 1 in. long, and then had two parallel flats machined over the gage length 0.085 in. apart. The test bars were annealed for 10 min at 700° F, and strained 1 pct in tension at room temperature. They were electropolished (80 pct acetic acid; 20 pct perchloric acid, 70 pct concentration) at a temperature of 60°F at approximately 20 v. A grid, transverse or square, spaced 0.2 mm apart, was impressed by rolling a fine threaded screw (128 threads per in.) across the flat surfaces. The depth of the grooves was less than 5 p. For final annealing and grain size control the specimens were enclosed in aluminum foil and sealed in Vycor tubes. Annealing conditions varied from 1 hr at 700° F to 5 days at 1050° F, depending on the alloy content, to give for most of the specimens a final grain size of about 1 mm. This treatment was followed by electropol-ishing as described above. For the test series presented in Figs. 4 and 5 round specimens were used instead of flat ones, and fine machining marks served as marker lines instead of the impressed grid lines. Electropolishing was omitted. The major advantage is that the spacing of the machining marks is only about 1 u as compared to the 200 u of the impressed grid lines, permitting higher precision in strain measurements. Unfortunately the strain annealing necessary for grain size control also resulted in some preferred orientation of the grains. The preferred orientation of three arbitrary specimens was measured by X-ray diffraction methods and the averaged results are shown in Fig. 1. The possible effects of the preferred orientation on the test results will be discussed later. The testing temperatures were 410°, 515", 725", and 940° F, with one exception in the case of the 5.1 pct Mg alloy. Since the solubility limit of this alloy is 520°F, a test temperature of 545°F was cho-se sen instead of 515°F. The selection of the test temperature was based on two considerations: 1) at 900°F and above, extensive grain boundary migration made it more difficult to measure grain boundary sliding; 2) at 400°F and below, there was so little grain boundary sliding that it was again difficult to make precise measurements. The stress was chosen to give a creep rate of approximately 2.7 pct per hr in connection with Figs. 2

Jan 1, 1961

By V. R. Garfias

Even before the arrival of Cortes in 1519, the history of Mexico was closely linked to that of its mineral production; the mining activities of the Aztecs being thus described by Clavigero, one of the early historians: In the mountains of Anahuac there abound in veins all kinds of metals, and infinite variety of other fossiliferous products. The Aztecs obtained gold from the countries of the Cohuijques, of the Mixtecas, of the Zapotecas and from various other places. They gathered that precious metal usually in gain, from the sands of the rivers, keeping a certain portion for the crown. They obtained silver from the mines of Taxco, of Tzumpango and others; however, this metal was not as esteemed by them as by other neighboring nations. They had two kinds of copper; one hard, which they used instead of iron to make sickles, lancea and all kinds of rural and military instruments and another, soft, with which they made kettles, goblets and other receptacles. This metal abounds mainly in the province of Zacatula and in that of Cohuijques, which at present is in the kingdom of Michoacan. They obtained tin from the mines of Taxco and lead from those of Izmiquilpan, located in the country of the Otomies. From the tin they made money, and the lead, we know they sold in the market places, but we ignore the uses to which they applied it. They also had mines of iron in Tlaxcala, in Taxco and in other places; but they either had not discovered them, or did not know how to make use of the metal they contained. In Chilapa there were mines of mercury, and in other places there were mines of sulphur, alum, vitriol, cinnabar, cohre and of a white earth which they esteemed highly. As regards mercury and vitriol, we do not know of what use they were to them; the other metals they used in paintings and dyes. There were then great abundance of amber and asphalt—bitumen of Judea—on the coast of the seas and many cities of that territory paid tribute of one and the other to the kingdom of Mexico. They mounted the amber in gold, and it was only used as ornament and display by them. With the asphalt they made certain perfumes. The following extracts dealing with pre-Colonial gold are taken from the famous " Cartas de RelaciÓn " to Charles V, in which Cortes described the progress of the Conquest: . . . here there came two chiefs who owned lands in the valley; one four leagues down the valley and the other two leagues up the valley and they gave me some gold necklaces of little value and seven or eight girls. . . . . . . that day I left the City of Churultecal and traveled four leagues to some villages of the City of Cuasucingo where the natives received me very well and gave me women and pieces of gold. . . .

Jan 1, 1937

By Thomas A. Read

THE internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of l00 when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose-that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals will be presented. EXPERIMENTAL PROCEDURE The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrement A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were .made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders ¼ in. in diameter and 1 ½ to 2 ½ in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is ¼ in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;''2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.' The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969

By J. W. Fredrickson

VERY little information is available in the literature concerning the solubility of magnesium in titanium. Aust and Pidgeon&apos; report the solubility of titanium in magnesium to be 0.0025 pct at 650°C and 0.015 pct at 850°C. X-ray diffraction studies failed to detect any evidence of solid solubility. Based on the fact that the addition of titanium to magnesium increases the c/a ratio of magnesium, Busk&apos; suggested that the Mg-Ti system, like the Mg-Zr, is a peritectic. Eisenreich- eported the solubility of titanium in magnesium to be 0.003 pct at 655°C and 0.064 pct at 760°C. Removal of hydrogen from the melt increased the solubility of titanium to 0.115 pct at 800°C. Eisenreich proposes a peritectic-type diagram for the high magnesium side of the system. Recent work&apos; with Ti-Mg diffusion couples indicate that the solid solubility of titanium in magnesium is extremely small and that there is limited solid solubility of magnesium in titanium. Experimental work on the Ti-Mg system is complicated by the fact that the boiling point of magnesium is considerably below the melting point of titanium. Consequently, the usual alloying methods are impractical. Alloying was accomplished in this investigation by sheath-rolling compressed compacts." The alloys were made from titanium sponge and high purity magnesium. Chemical analysis of the sponge showed 0.04 pct Mg, <0.005 pct Al, <0.001 pct Cu, 0.05 pct Fe, 0.022 pct Mn, <0.0025 pct Ni, 0.007 pct Si, <0.005 pct V, and <0.01 pct Zn. All heat treating was conducted in a protective atmosphere by encapsulating the specimens in fused silica ampules under a partial pressure of helium. Equilibrium was achieved by holding the specimens at temperature for periods of 24 to 120 hr. The alloys were hot rolled, cold rolled, and annealed prior to solution heat treatment. Fig. 1 shows the constitutional diagram obtained for the Ti-Mg system up to 1.5 pct Mg. Oxygen was known to be present in the alloys; therefore, it is necessary to consider the alloys as ternary rather than binary and the diagram should be viewed as a plot of a section through the Ti-Mg-0 system. Other investigatorso have shown that the addition of oxy- gen to titanium stabilizes the a phase. The data presented in Fig. 1 indicate that the addition of magnesium to titanium tends to stabilize the p phase. Armour Research Foundation7 has shown that the addition of magnesium to zirconium lowers the a transus and is classified as a p stabilizer in that system. Magnesium is soluble in solid titanium to the extent of at least 1.5 pct in both the a and /3 phases. No intermetallic compounds or magnesium-rich phases were observed either by light microscopy or X-ray diffraction. However, this does not negate the possibility that such phases exist at higher alloy concentrations.

Jan 1, 1956

By G. C. Gardner

A new correlation of blast penetration in model and operating blast furnaces is presented which overcomes objections to prevzous correlations. It is shown that the tuyere diameter is only of small importance in determining the magnitude of the penetration. The data from operating furnaces correlate satisfactorily with the data from models whose cross section is a segment of a circle. A bubble-shaped gas space called a "raceway" normally exists in front of the nose of a blastfurnace tuyere. The periphery or "wall" of the raceway is well defined and is composed of densely packed charge particles. The blast. issuing as a jet from the tuyere, entrains gas from the raceway, in the usual manner of a jet, as it flows to the opposing wall. There it divides and flows back around the walls to be entrained once more. The blast must, of course, eventually leave the raceway and pass up through the charge column, but before it does it may, on the average, make several circuits of the kind described and in doing so it carries with it charge particles, which, because of their fast and circulating motion, suggested the name of "raceway". A fuller description of the raceway may be found elsewhere."&apos; Here it is only necessary to mention, in addition, the measurement which characterizes its size. If an iron bar is pushed through the opened peepsight of a tuyere, .as far as it will go with ease, it will be stopped by the relatively impenetrable opposing raceway wall arid the distance that the bar has been pushed from the tuyere nose is called the "penetration". This measurement may be of practical importance and has; been the subject, with considerable success, of several attempts at correlation with other variables2-5 as stated in the next section. There is still, however, a serious objection to the most recent correlation,3 which is overcome by the correlation proposed in this paper. It will be shown that the objection is not trivial, in that the new correlation will attribute considerably different importance to the variables affecting the magnitude of the penetration. The data to be treated were made available by Wagstaff and are the same as those used in his correlation. They include measurements taken on small models, in which a cold air blast was used and no combustion occurred, and they also include data from operating blast furnaces at Wheeling and Fairless. The information from the blast furnaces will be shown to be in substantial agreement with those models whose plan views are segments of a circle and which are thus like segments of a blast furnace. First, Wagstaff&apos;s most recent correlation3 will be discussed and the objection will be given. Then the new correlation will be developed and its implications considered. CORRELATION OF J. B. WAGSTAFF Wagstaff&apos;s correlation is where and D — the penetration D,-the internal tuyere diameter V —the blast velocity in the tuyere

Jan 1, 1961

Discussion of the paper of E: D. Gardner, presented at the Salt Lake meeting, August, 1914, and printed in Bulletin No. 91, July, 1914, pp. 1467 to 1471. H. V. WINCHELL, Minneapolis, Minn.-There are two questions I should like to ask: First, does the Department still adhere to the decision made in the East Tintic case? Second, does the Department require placer ground to he of such value that, in the opinion of the Forest Service employees, it will pay to work, before admitting the location to be valid? T. C. HOYT,* Ogden, Utah.-With reference to the first question: the Department does not hold to that decision, as it was reconsidered by the Secretary Of the Interior, and the Department is governed by the decision of the Secretary Of the Interior, on those points always. The Department of Agriculture makes no decision as to what constitutes a sufficient discovery. The mineral examiners simply report their findings and Opinions. These are transmitted to the chief of the field division of the General Land Office, who in turn transmits the reports to the Commissioner Of the General Land Office, who decides whether the report raises an issue requiring a hearing. If a hearing is ordered, expert testimony is given on the question of the discovery, as well as the evidence of practical people who operate in the vicinity of the claim in question. As to the extent of placer values considered sufficient to justify a location, my answer will need a little amplification. I couldn&apos;t answer it directly for the reason that sometimes people resort to placer claim location as a means of acquiring land for Other purposes than placer mining, which makes it absolutely necessary that the government give close attention to the question of whether good faith has been shown, as it is the evidences of good faith that largely determine whether a report adverse to a claim shall be made. That is a difficult point to cover sometimes. For instance, in the region I have recently visited there are some 17 miles of a valley, from ¼ to ¾ mile in width, all covered by placer locations. It is valuable stock-grazing land, and is stocked at the present time. It also contains a stand of timber, and is on the watershed of an important stream-important from the fact that it furnishes the water supply to government storage reservoirs, and to pending reclamation and Carey Act projects. In this case the placer claims will not be disturbed as mere locations. They will simply remain there, and there will be no action with reference to them until the claimant asks for patent or, before patent, begins to denude that watershed and remove that timber. Then the government would direct that the mineral experts go on to the ground, examine it, prospect it, and submit their report, with a view to seeing if

Jan 11, 1914

US 4,137,751-Aerial geophysical exploration for ore deposits by collecting and analyzing atmospheric particulates The aircraft has an Inlet duct extending outward and including a "shave-off" duct, a cyclone separator located inside the cabin which is coupled to the inlet duct, a clean air exhaust duct, and a receiver for the collected particles incoming air is divided into two fractions. The fraction taken by the "shave-off" duct and containing the bulk of the particles is routed to the cyclone Particulates are gathered on a collector tape for subsequent analysis and correlation with the areas covered J. R Rhodes, R D. Sieberg, M. C Taylor, J. C Westkaemper, and R C. Young, assigned to Columbia Scientific Industries, Inc Feb. 6, 1979 7 pp. (73-28) Filed- 2-28-75 (554,114) Same British 1,446,760, dated Aug. 18, 1976. US 4,156,138-Exploration for subsurface deposits of uranium ore Pairs of dosimeters are placed underground in a grid pattern Each dosimeter contains a phosphor which IS capable of storing the energy of alpha particles. One dosimeter is heavily shielded from alpha particles, while the other in the pair is thinly shielded to exclude dust After a period underground the dosimeters are heated to release the stored energy as light. The amount of light produced from the heavily shielded dosimeter is subtracted from the amount of light produced from the thinly shielded dosimeter to give an indication of the location and quantity of uranium underground This patent is a division of US Patent No 4,053,772, dated Oct 11, 1977 P E Felice, assigned to Westinghouse Electric Corp May 22, 1979 5 pp (250-253) Filed. 8-12-77 (824,203) US 4,180,727-Method for measuring the gamma-gamma density of uranium ore in the vicinity of a borehole A first gamma-ray detector receives only natural gamma rays from the borehole, while a second receives both natural gamma rays and scattered uranium-source gamma rays The value of the uranium-source gamma rays is calculated. W W Givens, assigned to Mob11 011 Corp Dec 25, 1979 6 pp (250- 264) Filed 10-20-77 (843,909) US 4,180,72&A neutron activation probe for determining the location and grade of uranium ore, especially where thorium or other fissionable isotopes are present, includes a pulsed neutron source in series with a plurality of delayed neutron reactors for measuring radioactivity in a well bore- hole together with a Nal(T1) counter for measuring the high energy 2 62 MeV gamma line from thorium The signal from the Nal(T1) counter IS subtracted from the signal from the delayed source detectors to ascertain the amount of uranium present in the ore body N. P Goldstein and R C Smith, assigned to Westinghouse Electric Corp Dec 25,1979 6 pp (250-264) Filed. 4-1 1-78 (895,323)

Jan 1, 1980

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By M. E. Wadsworth, R. C. Peterson, W. M. Fassell

The temperature and pressure dependence of the reaction of tantalum in oxygen were investigated from 500° to 1000°C at pressures from 10 mm Hg to 600 psi total oxygen pressure. Tantalum was found to oxidize linearly under the above conditions. Three distinct regions of temperature dependence were found with different energies of activation. From 500° to 600°C the rate of oxidation of tantalum was found to be essentially independent of the oxygen pressure at the pressure investigated. The oxidation rate increases rapidly with an increase in pressure from 600&apos; to 800°C. The dependence of the oxidation rate on the bulk concentration may be expressed by V = k&apos;?, where k&apos; is the specific rate constant and ?=k1Co2/(l + K1Co2), where k, is the equilibrium constant for the adsorption of oxygen on tantalum. ONLY a limited amount of data has been presented in the literature on the oxidation behavior of tantalum metal. Some values of its oxidation rate were reported in the Corroston Handbook&apos; and by McAdams and Geil.&apos; The first extensive investigation of tantalum was the work of Gulbransen and Andrews." They determined the reaction rates of tantalum in O2 and N2. Their results indicate that this metal follows the parabolic law in the temperature range of 250" to 450°C in O2 at pressures of 7.6 cm Hg with an activation energy of 27,400 cal per mol. In nitrogen, the metal follows the parabolic law from 500" to 800°C at 7.6 cm pressure. All experimental determinations were of 2 hr or less duration and deviations from the parabolic rate conceivably could occur at longer times. A spectrophotometric study of the oxidation of tantalum by Waber, Sturdy, Wise, and Tipton&apos; indicated good agreement between this method and the microbalance technique. The experiments were conducted in air from 220" to 350°C. The metal was found to follow the logarithmic law up to 320°C and the parabolic law at higher temperatures. The activation energies in the logarithmic region were reported as 12.57 kcal per mol and 12.0 kcal per mol, respectively, for the microgravimetric and spectrophotometric methods. In the parabolic region the activation energy was found to be 27.2 kcal per mol, in good agreement with the value of Gulbransen and Andrews." The present paper is concerned with the behavior of tantalum from 500" to 1000°C in oxygen at pressures ranging from 1/2 to 40.8 atm pressure. Earlier preliminary data by McKewan5,6 indicated the following facts concerning the behavior of tantalum: 1—At temperatures from 500" to 600°C, the metal followed the linear law. 2—At 575°C the rate of oxidation was found to increase with O2 pressure. 3—The Arrhenius plot in this temperature region was nonlinear. The nonlinearity of the Arrhenius plot was indicative of a more complex behavior than originally suspected for this metal.

Jan 1, 1955

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By R. J. Grissom

PHOSPHATE deposits have been worked in many countries of central and south central Tennessee, but only ht ebrown rock deposits of Maury and Giles Counties will be discussed at any length in this articles, as all of the major opeations are now located there. They are: Mt. Pleasant District-Federal Chemical Co., Hoover and Mason Phosphae Co., International Minerals and Chemical Corp. (Maury and Giles Counties), Virginia-Carolina Chemical Corp. (formerly Charleston Mining Co.), and Victor Chemical Co. Columbia District-Armour Fertilizer Works and Monsanto Chemical Co. In the near future, the well-known, extensive deposits of blue rock in Lewis and Hickman Counties,also the brown rock in Hickman, Willamson, Summer and Davidson Counties, will again come into production. Certain physical peculiarities of the Tenessee deposit have played an important part in the design and use of mining and milling equipment.

Jan 1, 1944