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F. C. LANGENBERGW.*at 8ertoivn,M ass. (written cliscussiont).-I am inclined to the view that the change in physical properties encountered in the material with which the authors are working is due to the relief of internal strains. The statement, on page 1.098 of their paper, calling attention to the fact that this phenomenon disappeared when the material was rolled into 1 7/8 -in. square billets is of particular interest. It is certain that the internal strains set lip by cooling in a small billet of this size would be much less than those produced in a billet having a larger cross-section cooling under the same conditions. The statement that the physical properties of a given test bar were materially changed by standing has been brought to my attention in connection with the testing of gun forgings. I have made a number of observations on forgings produced at Watertown Arsenal to ascertain whether any change in ductility was produced by the aging of the test specimens. The results were always negative, but this can be explained by the fact that ii gun forging is generally a forging that has been quenched and subsequently drawn at a relatively high temperature.

Jan 10, 1919

By M. H. Richman, E. S. Meieran

An analytical method is presented which enables the electron diffraction patterns from a twinned region to be indexed. The method has only been applied to (112) twins in bcc lattices, but can easily be adapted to other types of twinned lattices. Calculations of all twin spots, including those superimposed on matrix spots, is made possible by this method. SINCE the advent of transmission electron microscopy, the analysis of selected-area electron diffraction patterns has become very important in the interpretation of electron micrographs. Frequently, as in the case of some martensites, twinned areas are observed and give rise to complex diffraction patterns, which so far can be analyzed only for the simplest orientations of the thin foil specimen with respect to the electron beam. In order to simplify the analysis of twin patterns of more complex orientations, an analytical method was devised which is capable of predicting the positions of all reflections from both matrix and twin regions for all possible foil orientations. Although the method has only been applied to the case of bcc metals twinned about a (112) plane, it is equally applicable to other Bravais lattices. This method has been successfully applied to selected-area electron diffraction patterns of Fe-Ni and Fe-Ni-C martensites and drawn tungsten wire. PROCEDURE Imagine the reciprocal lattice corresponding to a bcc material, with each point hkl representing the crystallographic plane (hkl). Since the extinction conditions require that for this lattice, only reflections where h + k + 1 = even integer are allowed, the three dimensional reciprocal lattice is actually fcc. Since in real space twinned regions and matrix regions are mirrored across a (112) plane, the twinned reciprocal lattice is derived from the matrix reciprocal lattice by a rotation of 180 deg about a (112) direction. While it is possible to calculate how a point hkl will shift under a twinning transformation to a new point htktlt using only the reciprocal lattice based on the orthonormal vectors [100], [010], and [001], the calculations are greatly simplified if a new orthonormal coordinate system containing the twin axis is introduced. The twinning operation then becomes a simple rotation of 180 deg about a principal coordinate axis (in this case the twinning axis), and a retransformation back to the original reciprocal space will give the position htktIt of the twinned reflection.

Jan 1, 1963

By Frank A. Herald

Through the generous cooperation of the authors of the papers in this chapter, a great wealth of fundamental data is being made available. The same plan of securing and submitting data will be carried forward next year, with the hope of making a nearer approach to complete presentation of the data contemplated in the plan. In order to conserve space, we are printing below such footnotes as have general application to Table 1 in the papers in this chapter: Footnotes to Column Headings Table I In areas where both oil and gas are produced, unless gas is marketed outside the field, such areas are included in column headed "Oil." Manufacture of casinghead gasoline and carbon black is interpreted as outside marketing of gas. Production per acre is determined by dividing into the number of barrels of oil the sum of the number of acres assigned to "Oil" plus such number of acres of the total assigned to "Oil and gas" as represents the portion thereof occupied by oil. Wells producing both oil and gas are classified as "Poducing oil only" unless gas from them is marketed off the lease. W. water; G. gas; A, air. Bottom-hole pressures are preceded by "e." All other figures represent pressures at casinghead with well closed. P, paraffin; A, asphalt; M, mixed. 0 Cam, Cambrian; Ord, Ordovician; Sil, Silurian; Dev, Devonian; Mis, Mississippian; MisL, Lower Mississippian; MisU, Upper Mississippian: Pen. Pennsylvanian; Per. Permian; Tri, Triassic; Jur. Jurassic; CreL, Lower Cretaceous; CreU. Upper Cretaceous; Eoc, Eocene; Olig, Oligocene; Mio. Miocene; Pli. Pliocene. 6, sandstone: SH, sandstone, shaly; Ss, soft sand; H, shale; L, limestone; LS, limestone. sandy; C, chalk; A, anhydrite; D, dolomite; Da. arkosic dolomite; GW, granite wash; P, serpentine. Figures are entered only for fields where the reservoir rock is of pore type. Figures represent, ratio of pore space to total volume of net reservoir rock expressed in per cent. "Par" indicates that the reservoir rock is of pore type but said ratio is not known by the author. "Cav" indicates that the reservoir rock is of cavernous type; "Fis," fissure type. A, anticline; AF, anticline with faulting as important feature; Af, anticline with faulting as minor feature; AM, accumulation due to both anticlinal and monoclinal structure; H, strata are horizontal or near horizontal; MF, monocline-fault; MU, monocline-unconformity; ML, monocline-lens; MC, monocline with accumulation due to change in character of stratum; MI, monocline with accumulation against igneous barrier; MUP, monocline with accumulation due to sealing at outcrop by asphalt; D, dome; Ds, salt dome; T, terrace; TF, terrace with faulting as important feature; N, nose; 9, syncline. Information will be found in text as indicated by symbols: A, name of author, other than above. who has compiled the data on the particular field; C, chemical treatment of wells; G, gas-oil ratios; P, proration; U, unit operation; R, references; W, water; 0. other information.

Jan 1, 1934

By Jei Y. Choi, P. G. Shewmon

The surfrrce-diffusion coefficients (DJ for Aulg8 on (100) and (111) surfaces of copper have been determined between 1050" and 780°C using a new avuzlysis imd experimental procedure. The results are: D, has also been determined fm cua4 at 870°C, and the values found are 4.5 times larger than those measured by the grain boundary grooving technique for the same surface orientations. This difference is felt to result from the approximate nature of the mathematical solution used in the present work. Attempts to measure D, for silver on copper and silver surfaces indicated a means of matter transport different from surface diffision was dominant in moving tracer from the source out over the surface. Cnlculations and experiment both indicate that this is the flow of silver through the vapor phase which completely masks the much smaller flow due to surface diffusion. The previous self-difhsion studies of D, for silver and copper are discussed in terms of our own analysis and found to yield values of D, factors of lo5 or more greater than those found by the grain boundary grooving tech -nique. UNTIL about 5 years ago it was widely believed that the activation energy for surface diffusion, AH, , was less than that for grain boundary diffusion, AHb,, which in turn was less than that for diffusion through the lattice, AHz.' This was concluded from various evidence that D,> Db>Dl, and one tracer study of D, for silver on silver from which AH, was inferred.2 In 1959 Mullins and Shewmon demonstrated that D, could be determined from the kinetics of the growth of grain-boundary grooves.3 Using this procedure, Gjostein measured D, on copper between 800" and 1050°C and found that the activation energy was roughly equal to AHl .4 Subsequent work on copper,5" silver,',' and goldg between the melting temperature T, and 0.87 T, confirmed that AH, as determined using the grain boundary grooving or scratch-relaxation technique was equal to or greater than AHz. During the same period, Drew and Pye again determined AH, for silver on silver using a tracer techniquelo and a mathematical solution similar to that of Nicker son and arker.' Though the values of D, Drew and Pye measured at any given temperature were about 200 times smaller than those reported by Nickerson and Parker, they again found a low activation energy of about 10 kcal, or about one fifth that found at the higher temperatures with the mass transport technique. A distinguishing characteristic of these two previous tracer studies is that they have worked at low temperatures (-1/2 T,) where they felt volume diffusion was negligible and then analyzed these data as if all tracer atoms leaving the source flowed out into and remained in a homogeneous high-diffusivity surface layer of undefined thickness. This is totally different from the model used in the mass-transport studies or the studies of grain boundary diffusion, which assume the high-diffusivity surface layer to be only a few angstroms thick. If this latter model is applied to the earlier tracer studies, it is shown that the tracer has really pe!etrated into the lattice a mean distance of 1000A. Thus the tracer distribution observed after an anneal is thought to be due to the combined effects of surface and volume diffusion. Independent of the relative validity of the two models, it seems evident to us that any comparison of the values of D, as determined in these two ways is meaningless and misleading, since the values of D, and AH, obtained in these two ways would be totally different for the same physical distributions of tracer. Once the fundamental difference in the approaches of the two techniques is established, we are faced with the question of which model better approximates physical reality. Here all the evidence seems to be on the side of the ''thin surface layer" analysis. In fact, the authors of Refs. 2 and 9 do not argue for the "thick-layer model" we have described; they simply invoke it through the equation they use to calculate D, . The primary evidence for the thin-film approach is: a) grain boundary grooves and scratches widen in proportion to tU4 and Mullins' rigorous analysis shows that this is only valid for a surface layer which is quite thin relative to the width of the groove;11 b) all accepted or seriously discussed models of solid-vapor interfaces and high-angle grain boundaries assume that the disturbed region of the interface is at most a few a0 thick. With the above in mind, it was desirable to determine D, using a radioactive tracer and a "thin-

Jan 1, 1964

By Ira Joralemon

THE sampling of disseminated copper deposits has been described often but the method of combining assays, to give the true shape and value of the orebody as it will be mined has received less attention. As the ore mined during five or ten years at several of the great disseminated properties has averaged materially lower in grade than the published estimates, the question of the sampling and estimating of these orebodies seems timely. In this paper, attention is given particularly to factors that may cause errors in the final estimate. Sampling of diamond-drill holes, churn-drill holes, and underground workings is briefly described in the first part of the paper; then the method of combining assays to give the average grade and tonnage that will be mined is taken up in some detail. The necessity of study of the geology of the deposit and of probable costs is emphasized. Finally, the methods of calculating tonnages are outlined. DIAMOND-DRILL SAMPLING There are three main requisites for accurate diamond-drill sampling. First, the core should be removed and the hole cleaned out at the beginning of every sampling interval, usually 5 ft. (1.5 m.). After the rods are let down, water should be run through them until it becomes clear. The water must be clear before drilling starts. In this way the material knocked down from the sides of the hole by the descending rods is washed away, instead of being left to salt the sludge, sample.

Jan 2, 1922

By E. R. Parker, D. L. Martin

During the heat-treatment of silver specimens for tensile tests it was observed that the bars blistered and became brittle when heated in a hydrogen atmosphere. To check this unexpected result, a wide variety of commercial silvers were heated in hydrogen at 850°C. Only a few of the materials developed blisters, the most severe of which is the tube pictured in Fig. I. The microstructure of a cross section of the tube is shown in Fig. 2. The embrit-tlernent is extremely severe at the edge; the blisters result from the severe deformation of the surface material by large under- lying gas pockets. The effects resulting from hydrogen embrittlement of silver have been observed by numerous investigators over a long time l,2,3 although it was only recently that a clear explanation was offered.4 However, the damage resulting from hydrogen embrittlement has not been generally recognized; and it is of advantage to know more about this phe- 1 References are at the end of the paper.

Jan 1, 1943

By D. L. Martin, E. R. Parker

During the heat-treatment of silver specimens for tensile tests it was observed that the bars blistered and became brittle when heated in a hydrogen atmosphere. To check this unexpected result, a wide variety of commercial silvers were heated in hydrogen at 850°C. Only a few of the materials developed blisters, the most severe of which is the tube pictured in Fig. I. The microstructure of a cross section of the tube is shown in Fig. 2. The embrit-tlernent is extremely severe at the edge; the blisters result from the severe deformation of the surface material by large under- lying gas pockets. The effects resulting from hydrogen embrittlement of silver have been observed by numerous investigators over a long time l,2,3 although it was only recently that a clear explanation was offered.4 However, the damage resulting from hydrogen embrittlement has not been generally recognized; and it is of advantage to know more about this phe- 1 References are at the end of the paper.

Jan 1, 1943

By C. A. Hansen

ROASTING FERRUGINOUS ZINC-SULFIDE ORES IN 1912, Mr. J. B. Ideating was developing an electrolytic-zinc process for application to the ores of the Bully Hill mines of the General Electric Co. These ores consist of blende and pyrite so finely crystallized and so intimately mixed that no mechanical separation of the individual minerals had been found possible. The ore was reduced to about 60 mesh and roasted in a hand-rabbled reverberatory furnace preparatory to leaching with sulfuric acid. The extractions obtained were quite irregular, varying from a minimum of about 70 per cent. to a maximum of about 90 per cent. This irregularity led to the construction of a small electrically heated roasting furnace, and to the study of roasting under definitely controllable conditions. From time to time, these studies have been extended to other ores. Several commercial-plant operators profess to have gained useful information from the results of these studies and it is hoped that their usefulness may be extended by this publication. EXPERIMENTAL ELECTRIC ROASTING FURNACE The furnace used for experimental work is shown in Fig. 1. One fire-clay sagger, or pot, was set within another and the space between the two filled with Silox heat insulation. The hearth is a cast-iron plate with an imbedded ribbon of nichrome wire; this wire heater is connected to a potential regulator, which permits a very close voltage control. A mechanically driven arm is fitted with rabble blades so arranged that a uniformly thick ore bed may be maintained indefinitely. This arm is usually driven at about one revolution per minute but its speed of rotation can be varied as desired. Compressed air is led into the furnace through a meter, and it was found necessary to preheat the air in order to secure the definitely isothermal conditions sought.

Jan 8, 1919

By E. H. Citron

CLEANING fine coal in jigs is not new in Europe, where the feldspar jig is being used almost exclusively for this purpose. A feldspar jig operates with an artificial bed made up generally of feldspar or other hard rock material. Dimensions and specific gravity of this material must be of suitable values for good bedding qualities. For good efficiency, the size should range between 1x2 in. and 2x2x½ in. thick. The disadvantage of an artificial bed is that it is not mobile and must be replaced every so often with new material to obtain good cleavage characteristics. A semi-mobile bed has been developed to retain only a part of the feldspar on the sieve screen— the other part is drawn off with the refuse material, from which it is reclaimed and returned to the jig feed. Recirculating this feldspar rock offers definite advantages. However, in time it will lose its original shape because of wear, and new bed material must be added to the jig feed. The latest feldspar jigs arc generally air-pulsated, Baum-type jigs, although more than 70 pct of the feldspar jigs operating in Continental Europe are still of the piston type. These jigs are very popular in Europe, but they do require a great deal of time and attention. New Theory to Eliminate Artificial Bedding: At the preparation plants of Pittsburg & Midway Coal Mining Co. it has always been the contention that a small piston-type jig could be developed to clean fine 1/4x0-in. coal down to 28 to 60 mesh efficiently by obtaining and admitting bedding material from the present plant refuse circuit to the jig feed. This eliminates use of artificial bedding materials. The jig should incorporate these essential adjustable features as follows: Adjustable Sieve Screen A screen that can be raised and lowered to increase or decrease washing compartment depth. The sieve screen also can be set on an incline level, or decline. Adjustable Plunger Eccentric Length of stroke can be adjusted to increase or decrease pulsion and suction. Variable Plunger Speed Variable speed reducer for decreasing and increasing the number of strokes per minute. Water Distribution Adjustable baffle plate separating the plunger and sieve compartment so the water can be distributed uniformly over the entire sieve screen area. Refuse Ejector Special unique rubber-type refuse ejector gate operated by air and electrically controlled (as a conventional jig). Automatic Control Conventional float that measures the specific gravity of the coal-water refuse medium in the jig is of the submerged type. The float is mounted on a vertical stem held in position by two parallel arms. A movable weight regulates the effective specific gravity of the float. The float stem can be raised and lowered, having a graduated scale to indicate the depth of bed for the setting of the float. Hutch Drawoff Hutch material is drawn from the cell compartment to the elevator compartment by gravity. The first one-cell experimental jig incorporating all these features was built in January 1955 by Ore

Jan 1, 1959

By P. Somasundaran

Processing of fine particles in suspension is markedly affected by their state of dispersion/aggregation. In addition, tendency for a given component of the system to undergo selective aggregation or selective dispersion is an important property which may be put to use for processing. In this paper, principles governing flocculation, dispersion, and selective flocculation of mineral fines are discussed and then the role of major solution properties such as pH, ionic strength, etc. is examined.

Jan 1, 1980

By John S. Alexander

THE typical block coal of the Brazil (Indiana) District differs in chemical composition but little from the coking coals of Western Pennsylvania. The physical difference, however, is quite marked ; the latter has a cuboid structure made up of bibuminous particles lying against each other, so that under the action of heat fusion through- out the mass readily takes place, while block coal is formed of alternate layem of rich bituminous matter and a charcoal-like substance, which is not only very slow of combustion, but so retards the transmission of heat that agglutination is prevented, and the coal burns away layer by layer, retaining its form until consumed. This property permits the use of raw block con1 in the furnace but theo-

Jan 1, 1876

By John S. Alexander

The typical block coal of the Brazil (Indiana) District differs in chemical composition but little from the coking coals of Western Pennsylvania. The physical difference, however, is quite marked; the latter has a cuboid structure made up of bituminous particles lying against each other, so that under the action of heat fusion throughout the mass readily takes place, while block coal is formed of alternate layers of rich bituminous matter and a charcoal-like substance, which is not only very slow of combustion, but so retards the transmission of heat that agglutination is prevented, and the coal burns away layer by layer, retaining its form until consumed. This property permits the use of raw block coal in the furnace but theo-

R. W. Raymond, New York, N. Y.: Mr. Bain's introductory statement that there is a growing disposition on the part of the public " to change emphasis " in government from political equality " to " social justice " is somewhat vague; but I gather from his argument that he approves the growing disposition to which he refers, and that the " emphasis " which it demands involves a radical change in the policy hitherto pursued by the United States—the policy under which the Pacific States and Territories have been developed thus far. I do not understand how "social justice" is to be furthered by the sacrifice of " political equality," or how the change is to be effected by "emphasis." But I fancy that the beneficent and necessary

Jan 1, 1913

By Armand Bur, W. R. Reichenstein

Since coal is one of the largest cost items in the production of electricity, its analysis for heat value and composition has been the subject of intensive study. Sampling started with crude hand methods, out of the railroad car or barge or from moving conveyor discharge, and progressed to reliable mechanical in-plant sampling systems. The mechanical system takes its sample from a falling stream of coal such as a conveyor discharge or crusher discharge hopper. But this has a disadvantage in that the identity of the coal is lost. Coal is shipped to the user in train-loads, often made up of shipments from various mines. When the cars are dumped into hoppers and the coal conveyed to the power station, the various shipments become mixed because residual coal remains in hoppers and chutes.

Jan 5, 1959

By Petri Bryk, John Ryselin, Rolf Malmstrom, Jorma Honkasalo

THE theoretical possibilities for the realization of flash smelting have been known for a long time. Calculations concerning the same can be found in previously published literature,1 and suggestions for its accomplishment in practice are described in patents on the subject. Likewise a smaller number of practical test results are known. Autogenous smelting is closely connected with flash smelting, since in flash smelting techniques it is possible to use the heat evolved by oxidation of the sulfides for the smelting process to such an extent that under certain conditions smelting can proceed without additional fuel. However, in the event that insufficient heat is available from the oxidation of the sulfide concentrates, then additional heat may be supplied by preheating the air, using oxygen enriched air, on burning additional fuel with the concentrate.

Jan 6, 1958

By D. R. Parrish, T. M. Geffen, R. A. Morse, G. W. Haynes

Flow tests on small core plugs have indicated that a large amount of gas is trapped and not recovered by water flooding a gas sand. Instead of I to 15 per cent pore space, as is usually assumed, the residual gas saturation is 15 to 50 per cent pore space, and is thus of the same magnitude as residual oil after water flooding oil sands. A thorough investigation was made to ascertain that large amounts of residual gas actually remain in reservoirs after a water flood and that this condition is not merely a laboratory phenomenon. In field experiments, the amount of gas left in a watered-out gas sand was measured by use of a pressure core barrel and the residual gas saturation of two watered-out gas sands was determined by electric log evaluation. In the laboratory, an investigation was made of factors that could possibly cause the value of residual gas saturation as measured on small core plugs to differ from that in the reservoir, and the effect of these factors on the amount of residual gas saturation was studied. The factors studied include flooding rate, static pressure, temperature, sample size and saturation conditions before flooding All evidence established that a relatively high gas saturation is trapped in water flooded gas sands and that this residual gas saturation can be measured in the laboratory by tests on small core plugs. INTRODUCTION There. has been general agreement among engineers that very high recovery of gas could be obtained from natural reservoirs By water displacement. Gas recoveries of 80 to 95 per cent of the original gas in place have become the normal expectation in water drive fields. The assumption of high recovery has been based on: 1. low density and viscosity of gas compared with water; 2. the erroneous assumption that the flow relationship in a gas-liquid system where gas is the displaced phase will be the same as when it is the displacing phase. It has long been recognized that gas can flow at very low gas saturations (in the range of 1 to 15 per cent pore space) in systems where liquid is being displaced by gas. By assuming the reversibility of this process, the conclusion was reached that the residual gas saturation following water flooding of a gas reservoir would be the qame (1 to 15 per cent) as that at which gas first flowed continuously as a displacing phase. Recent laboratory relative permeability Studies have demonstrated that the flow characteristics are very different in gas-liquid systems, depending on whether gas is displacing or being displaced by, a liquid. Also, it has been shown that there is no difference between the flow characteristics of oil and water or gas and water in water wet porous rocks. The residual gas saturation that can be expected following water flooding of a gas reservoir then would be in the same range as the residual oil saturation normally expected after water flooding an oil reservoir! i.e., in the range of 15 to 50 per cent pore space, depending on the rock characteristics. Obviously, such a difference in residual gas saturation means very important differences in recoverable gas reserves from water drive reservoirs. For example, if the original gas saturation in a field were 70 per cent, and the residual gas following flooding were 35 per cent, only half of the gas in place could be recovered by complete water drive, compared to the previously expected 80 to 95 per cent. This is a situation in which complete pressure maintenance could result in very greatly reduced recovery, since straight pressure depletion recoveries from gas reservoirs can approach 80 to 90 per cent. Such a change in thinking must be based on more complete information than a series of small core tests. Hence the work reported herein was undertaken with the objective of determining whether or not residual gas saturations indicated from small core relative permeability tests at atmospheric pressure and room temperature are representative of the residual gas saturations which could be expected after water flood of natural reservoirs. A study was made both through laboratory and fields tests to determine any differences in residual saturation which might be occasioned by differences in pressure, temperature, rate of flooding, and original saturation conditions. Four separate types of laboratory experiments and two field mesurements were made in this investigation. The apparatus and testing methods of each will he discussed individually. LABORATORY EXPERIMENTS, APPARATUS AND PROCEDURE Relative Permeability Tests Steady state flow experiments Here conducted using the Penn State type apparatus. The equipment used has beer (described in a previous publication? "Irreducible" water satu-ration was established in the core' by imposing ,a capillary pressure of 45 psi before simultaneous flow of air and water

Jan 1, 1952

By W. A. Backofen, R. L. Fleischer

AN effect of orientation on the creep behavior of aluminum at 4.2 OK has been observed. Stress relaxation was measured in a hard-type tensile device after stopping the drive. From the spring constant of the device the load-time record could be converted to strain as a function of time. The strain sensitivity was 2-10-=, and the usual creep time of 1 min normally allowed a stress drop of about 25 g per sq mm. Further details of the apparatus and sample preparation appear elsewhere.' It should be noted that neither stress nor strain were constant, so that quantitative comparison with current creep theories will not be made. Shear strain (y) as a function of time (t) was consistent with logarithmic behavior: y = A In t, where A is a constant. In some cases t was made as large as lo3 sec. In the results the quantity A divided by t (the resolved shear stress, which is the driving force for creep) is plotted as a function of strain prior to creep. The quantity A/t is thought to indicate qualitatively the ease with which dislocations can move during creep. In Fig. 1 are drawn tensile stress-strain curves and A/T-strain measurements for single crystals of three orientations: l(a) and l(b) for the maximum resolved shear-stress orientation, l(c) for an orientation 2 deg from [211], and l(d) for a [111] stress axis. The following observations were made: 1) At low strains the A/t values are nearly the same for the three orientations. 2) As strains increase, A/t drops most rapidly for [Ill.] and less rapidly for [211], while for the maximum shear-stress orientation it is constant during easy glide and drops abruptly at the termination of easy glide. 3) In stage 11, A/t values are again approximately the same for the three orientations. These observations are regarded as evidence that 1) the initiation of slip produces obstacles of essentially the same effectiveness for all of these orientations, while 2) the rate at which slip obstacles are produced before stage I1 is fully developed is strongly controlled by the amount of slip on more than one system. This second statement is consis-

Jan 1, 1961

By E. J. Rapperport, J. P. Pemsler

We have made calculations to evaluate the sensitivity of atomic absorption as a technique to measure vapor pressure changes with temperature. Our conclusion, supported by the experimental findings presented in this work, is that the ultimate sensitivity of the technique is well below lo-' Torr. This magnitude of vapor pressure sensitivity makes the method extremely attractive for thermodynamic studies. Atomic absorption techniques have been used previously in this connection by Scatchard and Boyd' and by vidale2 with a much lower sensitivity reported. Scatchard and Boyd's work measured cadmium pressure over Ag-Cd alloys in the range 0.02 to 0.3 Torr, and Vidale estimated that sensitivities of only 10"5 to 10"6 Torr are to be expected. Atomic absorption appears to be particularly well-suited to thermodynamic studies for several reasons: A) It is extremely sensitive; our experiments indicate an ability to measure vapor pressure changes of 10"9 Torr. B) It is highly selective; there is seldom interference among the resonant wavelengths of the various species. C) It may be performed in an absorption cell under static conditions. This alleviates such problems as surface impoverishment of alloys, attainment of equilibrium, and temperature measurement and control. D) Simultaneous, or near-simultaneous, vapor pressure measurements may be made for several elements in a given system. Experimental. The physical basis of the technique is the highly selective absorption of particular wavelengths by specific atomic species. In most atomic absorption work the element of interest is incorporated into a hollow cathode lamp to provide a characteristic spectral source of high intensity. The spectra lines characteristic of the element in the cathode are attenuated by atoms of that element in the radiation path. Radiation from silver or cadmium hollow cathode lamps was directed along a path containing a 10-cm evacuated silica cell. The cell was positioned within a silica windowed furnace and contained silver, cadmium, or an Ag-Cd alloy. As the furnace temperature was elevated, the number of atoms of the absorbing element in the vapor phase within the cell rose, and the resonant radiation was increasingly absorbed. Intensities were measured by passing the radiation through a Techtron Model AA-4 one-half meter grating atomic absorption spectrometer equipped with a photo-multiplier detector. In order to minimize instabilities in the source, the hollow cathodes were allowed to warm up for several hours and were run at only 2 5 to 30 pct of their maximum rated amperage. In addition the attenuated beam was monitored before and after each reading. The attenuation of resonant wavelengths may be related to vapor pressure by the following relationships.

Jan 1, 1969

By William A. Johnson

IT was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomogeneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot he obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yields information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most important types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in a gold-lead

Jan 1, 1942

By A. William Johnson

It was pointed out in an earlier paper1 that our understanding of the atomic mechanism by which diffusion occurs in metallic alloys is scarcely in an advanced state. This unsatisfactory condition is the result not of any lack of interest, but of the difficulty of designing experiments that .will yield suitable data. The diffusion coefficient of an alloy, measured in the usual way, is simply a number specifying the rate of homogenization of a nonhomo-geneous metal; this number, of itself, can furnish neither the rate at which the individual atoms move nor information as to the mechanism by which they move. It does not necessarily follow, however, that such information cannot be obtained, even if the path to be followed is still not clear. Much success has been attained in the study of diffusion in ionic crystals. A number of experiments, for which there are few counterparts in connection with metals, yield information often indicating a detailed mechanism by which diffusion probably occurs. From such work, quite acceptable theories of lattice imperfections have been developed by Wagner, Schottky, Frenkel, Jost and others.2 It is postulated that real crystals of stoichiometric composition contain, in equilibrium, certain imperfections of which the most importarlt types are: (I) vacant cation sites, with an equal number of interstitial ions; (2) vacant anion sites, with an equal number of interstitial ions; (3) equal numbers of anions and cations in interstitial positions; (4) equal numbers of vacant anion and cation sites. The classification of a particular crystal according to this scheme then follows from studies of the variation of electrical conductivity with pressure of the electronegative component surrounding the crystal, with ion size, and with temperature; other physical phenomena, such as the Hall effect, have aided in establishing the classification. The relative mobility of the anion and cation may be determined by chemical analysis of the salt at the electrodes following electrolysis. With such information, and knowing that one ion never occupies the lattice site normally belonging to an ion of opposite sign, it is usually possible to ascertain the diffusion mechanism. It is clear that the same experiments are not applicable to metal crystals, and substitute experiments that yield as much information have not yet been devised. Much can be learned, however, about the mobilities of the two* kinds of atoms in alloys by the use of radioactive metals as indicators. Only one such experiment has been performed in the past. In 1933, Seith and Keil,3 in an effort to explain the great difference between the rate of diffusion of gold in lead and of lead in lead, measured the rate of diffusion of radioactive lead in 3 gold-lead

Jan 1, 1942