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By J. D. Miller, J. E. Sepulveda

Tar sand deposits in the state of Utah contain more than 25 billion bbl of in-place bitumen. Although 30 times smaller than the well-known Athabasca tar sands, Utah tar sands do represent a significant domestic energy resource comparable to the national crude oil reserves (31.3 billion bbl). Based upon a detailed analysis of the physical and chemical properties of both the bitumen and the sand, a hot-water separation process for Utah tar sands is currently being developed in our laboratories at the University of Utah. This process involves intense agitation of the tar sand in a hot caustic solution and subsequent separation of the bitumen by a modified froth flotation technique. Experimental results with an Asphalt Ridge, Utah, tar sand sample indicated that percent solids and caustic concentration were the two most important variables controlling the performance of the digestion stage. These variables were identified by means of an experimental factorial design, in which coefficients of separation greater than 0.90 were realized. Although preliminary in nature, the experimental evidence' gathered in this investigation seems to indicate that a hot-water separation process for Utah tar sands would allow for the efficient utilization of this important energy resource. The projected increase in the ever-widening gap between the domestic energy demand and the domestic energy supply for the next few years has motivated renewed interest in energy sources other than petroleum, such as tar sands, oil shale and coal. Although a number of research programs on the exploitation of national coal and oil shale resources have already been completed, very few programs have been initiated on the processing of tar sand resources in the United States. In recognition of their significance as a domestic energy resource, investigators at the University of Utah have designed an extensive research program on Utah tar sands. An important phase of this program, and the main subject of this publication, is the development of a hot-water process for the recovery of bitumen from Utah tar sands, as a preliminary step toward the production of synthetic fuels and petrochemicals. The term "tar sand" refers to a consolidated mixture of bitumen (tar) and sand. The sand in tar sand is mostly a-quartz as determined from X-ray diffraction patterns. Alternate names for "tar sands" are "oil sands" and "bituminous sands." The latter is technically correct and in that sense provides an adequate description. Tar sand deposits occur throughout the world, often in the same geographical areas as petroleum deposits. Significantly large tar sand deposits have been identified and mapped in Canada, Venezuela and, the United States. By far, the largest deposit is the Athabasca tar sands in the Province of Alberta, Canada. According to the Alberta Energy Resources Conservation Board (AERCB),2,3 proved reserves of crude in-place bitumen in the Athabasca region amount to almost 900 billion bbl. To date, this is the only tar sand deposit in the world being mined and processed for the recovery of petroleum products. Great Canadian Oil Sands, Ltd. (GCOS) produces 20 million bbl of synthetic crude oil per year. Another plant being constructed by Syncrude Canada, Ltd. is expected to produce in excess of 40 million bbl of synthetic crude oil per year. According to the Utah Geological and Mineral Survey (UGMS), tar sand deposits in the state of Utah contain more than 25 billion bbl of bitumen in place, which represent almost 95% of the total mapped resources in the United States.4 The extent of Utah tar sand reserves seems small compared to the enormous potential of Canadian tar sands. Nevertheless, Utah tar sand reserves do represent a significant energy resource comparable to the United States crude oil proved reserves of 31.3 billion bbl in 1976.5 Tar sands in Utah occur in 51 deposits along the eastern side of the state.4 However, only six out of these 51 deposits are worthy of any practical consideration (Fig. 1). As indicated in Table 1, Tar Sand Triangle is the largest deposit in the state and contains about half of the total mapped resources. Information regarding the grade or bitumen content of Utah deposits is still very limited. The bitumen content varies significantly from deposit to deposit, as well as within a given deposit. In any event, the information available6-8 seems to indicate that Utah deposits are not as rich in bitumen as the vast Canadian deposits which average 12 to 13% by weight.9 Although many occurrences of bitumen saturation up to 17% by weight have been detected in the northeastern part of the state (Asphalt Ridge and P. R. Spring), the average for reserves in Utah may well be less than 10% by weight. Separation Technology As in any other mining problem, there are two basic approaches to the recovery of bitumen from tar sands. In one

Jan 1, 1979

By Donald Barton

THE purpose of this torsion balance survey and the quantitative calculations was to delimit the extension of the cap rock at the Hoskins Mound salt dome. The sulfur ore in the Gulf Coast sulfur-bearing salt domes occurs in the lime rock, which is the outer layer of the cap-rock mass, and also in the underlying gypsum zone. The status of the exploration and exploitation of the Hoskins Mound dome at the date of this survey is shown by Fig. 1. The mound had been covered by the very early prospect wells of the Mound Oil Co., and the later and more numerous prospect wells of The Texas Company. The Freeport Sulphur Co. was producing from the flank wells in the southwest quadrant. The limits of the cap were surmised to lie inside the centers of quad-rangles 4F, 3F, the center of the NE. ¼ of 2E, and the north line of 2D. That surmise was based partly on the data of Fig. 1 and partly on the position of the edge of the topographic mound. The management of the Freeport Sulphur Co. wished to block out the extent of its ore reserves with a minimum of expenditure. The management was informed by the writer that no geophysical method could map the presence or quantity of sulfur directly, or determine the presence and quantity of the lime-rock cap independently of the rest of the cap, but that a reasonable probability existed that the approximate position of the edge, the depth and the thickness of the cap-rock mass as a whole could be determined through quantitative calculations based on the data of a very careful torsion balance survey. Considerable lime rock would probably be present, of course, wherever much cap rock was present. This paper presents the data of the survey, our calculated prediction of the configuration of the cap rock, and the degree of confirmation by the subsequent drilling. The survey was made by the Geophysical Research Corporation, under the direction of the writer. The work of the calculations was done by Andrew Gilmour, then assistant to the writer.

Jan 1, 1936

By John Croston

IN the closing months of 1936 the copper industry gave every evidence that it was at last on the threshold of an improved era. At the beginning of the year prices stood at 9 1/4¢, which in itself was a great improvement over prices prevailing for the three previous years. Industry generally was showing signs of moving forward in this country, and business was definitely good in certain foreign quarters. The threat of war and prep-arations for rearmament in Europe and Asia acted as a further stimulus purchasing. By midsummer the situation had so improved and stocks to been so reduced that the cartel of foreign producers (including American producers with foreign mines) decided to increase the produc-tion quota to 75 per cent on Aug. 1. Large-scale buying gave continued strength to the price and by Oct. 1 the quota was increased to 80 per cent, and again on Oct. 15, to 85 per cent. Notwithstanding this the price of copper continued its advance and on Nov. 1, with stocks declining con-tinuously, the cartel increased operations to 95 per cent, then to 105 per cent on Nov. 5. In the meantime the domestic producers, because of the great increase in home consumption, had increased their production by nearly one-half. At the close of the year copper sold at 120 per pound, and since the turn of the present year has reached 170. This rapid increase has not been wholly justified. Much of the increase was due to the legitimate demands of recovering industry, but rearmament orders plus accumulation of reserve stocks in case of war, purchases in anticipation of labor strikes and purely speculative activities on the London Metal Exchange accounted for the balance. Certainly in view of the state of industry and the general world price level, it appears unnecessarily high. Talk of a copper shortage is sheer nonsense, the recent condition in the market being created by overbuying, leaving but a small volume for speculative supplies. It takes some months for an increase in mine output to reach the market, but production is again overtaking apparent consumption, stocks have begun to increase, and this, together with the reopening of many small

Jan 1, 1937

By Thomas Read

READJUSTMENT Of the industrial world to a peace .basis after more than 4 years of war will involve many fundamental and far-reaching changes that cannot as yet he clearly foreseen or definitely provided for. Such problems may be subdivided, in the vocabulary of war, into those involving material and those centering about personnel. Of the two, the-latter group is the more difficult and obscure, as the factors involved are less clearly understood and the methods to be followed are not yet tested and standardized. When it is said that the market is weak, stocks large, and demand light, every business man understands clearly what is meant and. what course he should adopt to adjust himself, so far as possible, to such conditions. But when it is said that the rapid spread of Bolshevism in Europe is a danger to industrial organization in this country, it is difficult to have any assured sense that all that the statement may mean is clearly understood or that the means to be followed to meet such a situation are definitely known. Since Bolshevism is primarily a mental phenomenon and since the rupture it brings about in industrial organization should be prevented, if possible, it is my purpose to restrict this discussion of the activities of the Committee on Industrial Organization to some of its mental aspects, as the chairmen of the sub-committees, from their special knowledge of their own fields, can best set forth recent progress in the lines with which they are especially concerned. The first requisites of success in industrial organization, as in the biological organism of which it is the social counterpart, are unity of purpose and coordinated activity. Typical good and bad examples of this are the relative parts that the United States and Russia have played in the great war. These two factors are primarily mental, and it is not difficult to view the mental aspects of all problems of industrial organization as the most important ones. Unless we can attain unity of purpose and coordinated activity in industry, the provision of comfortable homes at reasonable rent, the assurance of steady work at good wages, the

Jan 2, 1919

By E. S. Bardwell, R. J. Lapee

Twenty years ago, W. T. Burns, in his paper presented at the Butte Meeting of the Institute,' discussed the general scheme then in use in the electrolytic copper refinery of the Anaconda Copper Mining Co. at Great Falls, Mont., for removing impurities from tank-room electrolyte and controlling its acid content. Since then marked changes have taken place in copper-refinery practice at Great Falls. The electrolytic copper refinery in use in 1913 has been replaced by a new and entirely modern plant capable of producing up to 27,000,000 Ib. of cathode copper per month. With the building of the new plant in 1916, the treatment of converter anodes was discontinued. At first the substitution of refined anodes for converter anodes resulted in a decrease in the impurity content of the anodes, but as time went on, changes in metallurgical practices at the smelter resulted in substantial increases in the impurity content of the anodes. The leaching of the silver slime to remove copper before shipment to Raritan for treatment further added to the purification problem. The fact that the scheme of purifying electrolyte which Mr. Burns described in his paper has proved adequate for our needs under a wide variation of conditions speaks well for its essential soundness. Method of Purification Briefly, the method adopted for purifying tank-room electrolyte at Great Falls has been as follows: Each day a certain volume of tank-room electrolyte is run off and sent to the purification plant, where it is boiled down to approximately 46' 136. The concentrated electrolyte is then sent to crystallizing tanks where the bulk of the copper is crystallized out as copper sulfate. The mother liquor is then passed through insoluble anode tanks to remove the last of the copper and most of the arsenic and antimony. It is then either returned to the tank room direct or boiled down to 55' Bé, the iron and nickel salts crystallized out and the mother liquor returned to the tank-room circuit as restored acid. Prior to 1930 all of the evaporating was done in lead-lined tanks 13 ft. in diameter by 4.5 ft. deep, provided with lead heating coils through which steam at 30 lb. gage pressure was circulated.

Jan 1, 1934

By J. J. Gilman, T. A. Read

FOLLOWING the deformation 01 zinc monocrys-tals, sharply bent basal planes are observed near several types of inhomogeneities. Three of these in-homogeneities have characteristics which are quite regular so that they can be studied and analyzed. These are compressive kink bands, "deformation bands," and the inhomogeneities near end restraints. The present paper describes experiments in which "deformation bands" were artificially produced, and bend plane phenomena are discussed in terms of dislocation theory. Also, two new bend plane phenomena are described. The importance of bend plane phenomena in the deformation of crystals is not widely recognized. Many phenomena may be explained in a manner similar to the discussion in this paper. Jillson1 has pointed out that the "punching effect" in zinc is a bend plane phenomenon and is not caused by prismatic slip.' Bowles3 has suggested that they may be involved in diffusionless phase changes. Cahn4 has discussed the role of bend plane formation in the polygonization of zinc. Experimental Work Tensile Kink Bands: Because of the geometrical similarity between "deformation bands" and "kink bands" (compare Fig. 1 of this paper with Fig. 1 of the paper by Hess and Barrett"), the band shown in Fig. 1 of this paper will be called a "tensile kink band," and that shown by Hess and Barrett will be called a "compressive kink band." It is felt that the term "deformation band" should be reserved for banded structures in polycrystalline materials such as iron." Tensile kink bands seem to form spontaneously in aluminum crystals deformed by tensile loading.7-10 In zinc and cadmium crystals they do not form in good, carefully loaded specimens.'." However, tensile kink bands can be produced artificially in zinc crystals. The present authors did this by scratching one of the flat surfaces of triangular crystals transversely with a sharp needle. Natural tensile kink bands caused by inhomogeneities sometimes appeared in deformed crystals which were identical in appearance with the artificially produced ones. Zinc monocrystals were grown by the Bridgman method in graphite molds. Chemically pure zinc (99.999+ pct Zn) was used and the molds were sealed inside evacuated pyrex tubes during growth. The crystal cross sections were equilateral triangles with a typical base of 0.210 in. The artificial kink band shown in Fig. 1 is typical of tensile kink bands in zinc. The band lies between two bend planes which run from upper right to lower left and is inclined oppositely to the slip bands which are sharply bent at the two bend planes. The general form of the artificial tensile kink bands was independent of the scratch depth (1 to 5 mils deep) and also independent of which side was scratched. These variables did cause variations, however. Deep scratches produced more localized kink bands than light scratches. Also, if the angle between the slip plane traces and a transverse scratch varied appreciably among the three sides, then localization of the resulting kink bands also varied. Furthermore, if the slip direction lay nearly parallel to the scratched side, the band was more developed near the scratched side than at the opposite edge. Scratches produced tensile kink bands for crystal orientations from xo = 15" to x, = 75". Fig. 2 shows a scratched crystal after deformation. One triangular side lies in the plane of the photograph. The right hand tensile kink band was produced by a transverse scratch on the upper right side. The next two kink bands were the result of scratches on the front surface. The kink band at the left was caused by a scratch on the lower back side. All four bands have the same general form. A longitudinal scratch was also made on the crystal shown in Fig. 2 to determine the effect of a scratch on the critical shear stress. The critical shear stress of the scratched region was 33.9 g per sq mm compared to 24.4 g per sq mm for the un-scratched region above it. Fig. 3 shows Laue patterns of the crystal shown in Fig. 2. Fig. 3a shows the pattern of the undeformed crystal. The orientation was x, = 21°, A, = 31". After deformation, Fig. 3b was made of the homogeneously deformed portion of the crystal. The spots are compact but split into two halves. This region was elongated 45 pct and its orientation was x = 14", X = 20"; the sine law predicts x = 14", A = 20.5". Fig. 3c was taken near the center of the middle tensile kink band of Fig. 2. The pattern shows a range of orientations and polygonization in this region. The spread in orientation was due to the fact that the basal planes were curved (see Fig. 1) rather than flat as in the ideal case. Some may also have been the result of elastic distortions and "local curvatures." The orientation range was x = 23" to 32", A = 30" to 42". It is apparent from Fig. 3 that the material inside and outside the kink band rotated in opposite directions with respect to the tension axis during deformation. The orientation calculated from the ideal configuration of Fig. 9,

Jan 1, 1954

By R. A. Wagstaff

Many changes in equipment have had to be made to handle the flotation products at the blast furnace, and these changes have meant an expenditure of considerable money, which has not been compensated by an increase in smelting tonnage. To date, very few new lead mines have been developed, so that the help derived by the innovation of flotation has been directed to old producing properties, where the ratio of concentration is greater now than when gravity concentration was in effect. In some smelting plants there has been an abandonment of complete units due to the introduction of flotation. Flotation Products Difficult to Handle The physical characteristics of the flotation product do not make for economic handling for lead blast-furnace work, either mechanically or metallurgically. The millman or miner do not know what trials and tribulations they have passed on to the smelterman. To the smelterman it is "the everchanging flotation," for little does he know what new reagent will be perfected tomorrow that may completely change the grade and physical characteristics of the product. Even the mining companies who have complete units of mining, milling and smelting have had a hard time to reconcile themselves to the fact that the unit cost per ton of ore smelted must go up with the increase of flotation product on the blast-furnace charge. The "smelterman's burden," for that is what flotation has been for the last few years, has not caused the smelter operator to lag or fall down, but has spurred him on with new zeal. The physical properties of the flotation products are as follows: (1) High moisture content; (2) mucky nature of product; (3) fineness of product, and (4) high metal content. New Mechanical Devices for Handling Furnace Product These characteristics have caused the use of many new mechanical devices in smelting practice, for example: New transportation equipment, such as solid-bottom cars, is required; unloading equipment and sampling

Jan 1, 1928

By S. B. Sargent, V. J. Collins, Lester C. Uren

[The conclusions arrived at by authors in paper read before the Petroleum Division and the California Sections of the Americam Institute of Mining and MetallurgicaI Engineers and the Standardization Division of the American Petroleum Tnstitute, at a joint session held at Los Angeles, Cal., Jan. 21, 1926, are presented below.] From the theoretical discussion and experimental evidence presented in this paper, the following conclusions may be drawn: 1. The efficiency of the oil-well plunger pump is dependent to an important degree upon the submergence provided. 2. Ample submergence must be secured in order to provide sufficient static pressure to force the oil through the restrictions interposed in the oil path at the standing valve and at the plunger nut surrounding the garbutt rod. These restrictions should be no smaller than is structurally necessary, in order to reduce resistance to oil flow to a minimum. 3. A part of the static pressure developed below the standing valve by submerging the pump is dissipated in overcoming the inertia and in providing upward acceleration for oil left between the pump valves at the conclusion of the down-stroke of the plunger, and of oil below the standing valve in the gas anchor above the oil inlet. This loss in effective static pressure can be reduced to a minimum by dispensing with the garbutt rod and placing the working valve at the lower end of the plunger. The valves should be as near together at the conclusion of the down-stroke of the plunger as is consistent with security in avoiding striking of the lower end of the plunger on the standing-valve crown. Gas anchors should be short, and oil inlets should be as near the standing valve as is consistent with proper gas exclusion. 4. Because of the presence of gas in solution in the oil, which tends to escape from solution under the reduced pressure conditions above the standing valve, the effective length of stroke of the plunger is reduced, and the suction effect of the rising plunger is largely nullified. The influx of oil through the standing valve is therefore chiefly dependent on static pressure developed by submergence.

Jan 1, 1927

The following Nominating Committee having been already appointed and approved by the Executive Committee in accordance with authority vested in the Executive Committee by the Board of Directors, was approved by the Directors: John V. N. Dorr, Chairman, Percy G. Beckett, J. W. Hutchinson, Julian Kennedy, William H. Linney, Charles W. Merrill, and E. Gybbon Spilsbury. The question of the purchase of Liberty Bonds, as well as that of bringing to the attention of the members the advisability of the purchase of these bonds, was referred to the Finance Committee. Sixty Members, four Associates, and thirty-six Junior Members were elected. Two Members were reinstated. Eight resignations were accepted.

Jan 7, 1917

By Eugene A. Stephenson

The writer apologizes for presenting this very elementary analysis of one aspect of proration, but a search of the literature failed to disclose any concrete illustrations of the effect of various proration formulas upon the allowable oil produced by tracts of different sizes. Many engineers have doubtless made somewhat similar calculations and are fully acquainted with the results. The various allocation formulas that are in use are based on one or more of the following factors: (1) wide-open well potential, (2) potential through an orifice, (3) uniform well allowable, (4) acreage, (5) sand thickness, (6) bottom-hole pressure, (7) productivity index, and (8) volumetric displacement. Of these, the unrestricted potential formula, or open-flow test, and the uniform well allowable are commonly regarded by engineers as those least likely to give each producer his proportionate share of the oil or gas, as represented either by acreage or by sand thickness, or both, except when the wells are located on tracts of large size. Unless the mechanical equipment that may be used during the potential test and the method of taking the test are both specified, the net result of the potential formula is to practically force the operators to use special equipment and adopt special procedures prior to and during the potential test, so as to secure the largest possible allowables. Much ingenuity and skill have been devoted to this,problem, but the general effect is to permit excessive allowables for very small tracts, and stimulate unnecessary drilling. It is interesting to compare some of the high yields from the Wilcox horizon at Oklahoma City with each other, as an illustration of the effect of an allocation factor based solely on potential (Table 5). One of the glaring instances is a well on a ½-acre lease, which had produced, as of September 1936, at the rate of almost 3,000,000 bbl. per acre. This is at least twice as many barrels as could have been present under the property if the reservoir had consisted of a tank of oil 200 ft, deep and 56 acre in area. Numerous combinations of acreage, potential, bottom-hole pressure, sand thickness, etc., have been proposed and are in use in various fields.

Jan 1, 1937

By Ben-Zion Weiss, Melvin R. Meyerson

FATIGUE crack propagation in some aspects can be viewed as being a result of localized plastic deformation concentrated near the tip of the crack.' Deformation is influenced by microstructure which in turn can affect the fatigue crack growth significantly. To study the effect of localized microstructural changes on fatigue crack propagation, cantilever-type notched specimens were subjected to cyclic bending at constant load amplitude. The extent of fatigue crack propagation was obtained by measuring the length of the crack by periodic observation with a microscope on the polished side of the sample,2"4 and these data were used in preparing the curves in the figures which follow. Figs. 1 (solid lines) and 2 show experimental results obtained in austenitic type 302 stainless steel containing higher than standard carbon (0.24 pct C) and 310 stainless steel. Both steels were homogenized for 8 hr at 1120°C and then water-quenched in order to prevent the precipitation of carbides. Fig. 3 shows experimental results obtained on 9440 low alloy steel in the normalized condition and in the quenched and tempered (580°C) condition. Indications of microstructural influence can be seen in scattering of the experimental data. The degree of scattering depends on both the microstructure and the amount of cyclic stress applied to the sample. For microstructures which are more easily deformed plastically, e.g., normalized or annealed as compared with hardened and tempered structures, the scattering is greater. Similarly, higher stresses produce greater scattering in the results, regardless of whether the cause of the stress increase is due to initial loading conditions or the growth in crack length. Scattering is believed to be a result of partial redistribution in the stress field around the tip caused by plastic deformation. This opinion is borne out by much smaller scattering of experimental results in the austenitic 302 high-carbon (0.24 pct C) steel. In this steel, plastic deformation in the neighborhood of the crack causes partial mar-tensitic transformation of metastable austenite,5 which in turn restrains further plastic deformation. As a result, the stress redistribution around The tip is reduced. Partial martensitic transformation was confirmed

Jan 1, 1969

By P. G. Shewmon, H. E. Collins

We have studied the effect of adsorbed sulfur on the surface self-diffusion of copper using eight diflerent surface orientations and the grain boundary grooving method. The eight orientations studied were the four lying near the low-index surfaces—(loo), (Ill), and two directions in the (110)-plus four higher-index surfaces. Surface-diffusion measurements were made over a range of HZS concentrations (in Hz) from 3 to 1500 ppm between 830°and 1050°C. The results can be divided into two groups—Group 1 contains the two (110) surfaces while Group 2 contains the remaining six surfaces. In Group 1, increasing the temperature increases the effect of Hz S on DS for the Hz S range 5700 ppvn. Qs and Do increase with increasing H2S concentration in this Hz S range. Beyond this range, increasing the temperature decreases this effect on D,; also Q, and Do decrease. In Group 2, increasing the telnperature decreases the effect of H2 S on D, for the H2S range studied, and Qs and Do decrease with increasing Hz S concentration. In any study of surface phenomena, there invariably arises the question of the possible presence of and effect of adsorbed impurities. Such questions are well-founded since the presence of adsorbed atoms can sometimes produce marked changes in the kinetics of surface-energy-driven processes. In the last few years, values of the surface self-diffusion coefficient, D,, have been determined on a variety of metals by studying the decay of scratches or the growth of grain boundary grooves.L~3-L0~L3 Yet there has been relatively little work done in which the concentration of an adsorbed impurity was systematically varied and the effects observed. Work of this sort would provide some basis in fact for the assertions often made about the ro1.e of adsorbed impurities in the differences between the results of different workers in different atmospheres and on different metals. It also is relevant to those cases in which surface monolayers produce profound effects in commercially important processes. The most marked example of such effects is the ability of nickel or palladium to increase the sintering rate of tungsten by many orders of magnitude.' The aim of this work was to study the effect of sulfur partial pressures on the surface self-diffusion of copper. It was felt that this in conjunction with a study of the degree of adsorption and type of active sites involvedL8 would provide a wide range of data for one system and hopefully lead to some insight into the mechanism by which sulfur adsorption influences copper diffusion. The main reasons for choosing the Cu-S system were, first, faceting was reported not to accompany the adsorption of sulfur. This is required if our experimental technique is to work. Second, Oudar has determined a high temperature adsorption isotherm for this system, an event which puts the Cu-S system almost in a class by itself.I4 EXPERIMENTAL PROCEDURE Initially, we considered studying the effect of an adsorbed impurity on surface self-diffusion of copper using isolated (or single) scratch smoothing as the technique and oxygen as the impurity. Copper was chosen as the material because the effects of orientation and anisotropy of the surface self-diffusion coefficient, D,, of copper in a dry hydrogen atmosphere had been studied extensively by Gjostein' and by Shewmon and ~hoi.~,~ The isolated scratch technique was chosen because both the effects of surface orientation and anisotropy of D, in a given surface could be easily studied with this method.~ Oxygen was tried as the impurity because Robertson and Shewmon""~ had studied its adsorption on copper at 1000°C over the range of oxygen partial pressures of 10"22 to 10-l3 atm. After several preliminary runs, it became evident that neither the scratch technique nor the impurity oxygen would be satisfactory for this work. Scratching deforms an annealed surface so that the region near the scratches recrystallizes, thereby disrupting the scratch profiles. One can avoid this by deforming the specimen sufficiently before scratching to give complete recrystallization on subsequent heating.4 However, as a result of Gjostein's success in scratching and annealing undeformed gold single crystals without local recrystallization,13 we attempted something similar with copper single crystals using a 0.7-mil diamond phonograph needle mounted in a Tukon hardness tester. All specimens recrystallized upon being annealed. Also, some copper specimens were sent to Gjostein to be scratched using his technique. The results were the same. As a result, the scratch technique was dropped in favor of the grooving of symmetric grain boundaries. Preliminary work using oxygen showed that faceting began to occur before oxygen adsorption had any measurable effect on D, at 938°C (at Pbo/P, = 0.12). Since heavy faceting would interfere with the measurement, we decided to use a sulfur-containing atmosphere (H2S/H2). Work by Oudar and Benard' and Robertson" showed that sulfur absorbed on copper and that faceting was not observed.

Jan 1, 1967

By E. R. Borcherdt

IT is notable that the first large-scale mine operation equipped entirely with detachable bits was the Badger State mine of the Anaconda Copper Mining Co. in Butte, Montana, just 30 years ago. This mine in 1922 was producing approximately 1200 tons of ore per day. Much of the data presented in C. L. Berrien's article' describing the development and installation of the Hawkesworth detachable drill bit were obtained from these operations. As in any pioneering effort, no precedent existed and many difficult problems required solution, so that the changeover to detachable bits at all Butte hill mines was not completed for 6 years. There was widespread disbelief as to the probable efficiency of the new installation. Some attempts were made in 1931 by the owners of the Hawkesworth patents to interest Ontario gold mine operators in the bit. These efforts were not successful, but they undoubtedly stimulated thinking which resulted in the invention and patenting of several well-known Canadian detachable bits, one of which is now a widely used throwaway bit. The success of the Butte installation also led to the development of the threaded type of bit connections by several well-known manufacturers, and in 1935 these bits were introduced to the mining industry on a national scale. The original Hawkesworth bit was not provided with a water hole but, depended upon water passing through the clearance opening between the tongue in the bit and the groove in the rod to flush cuttings from the drill hole, see Fig. 1. In December 1935 it was found that this method of introducing drilling water to the bit face resulted in high dust counts. To correct this a water hole was drilled on the central axis of the bit, passing through the tongue. Unfortunately, quenching water would rise through the small water hole, spot-hardening the tongue to cause breakage, never completely eliminated. In the fall of 1936 large-scale tests indicated that savings would be effected by use of a threaded type of bit, which was therefore adopted as standard for all Butte mines. This type of bit was used until 1947, when it was superseded by a one-use slip-on type. Since the first use of the Hawkesworth bit every detachable bit of importance has been investigated, and where advantages which might reduce costs or increase efficiency were indicated, substantial tests of the bit were carried on in the Butte mines. When tests demonstrated the advisability of changing from one kind of detachable bit to another the change was made at one level or in one area each day until the new rod and bit equipment was used throughout the mine. This involved a minimum of cost and disruption of drilling. Intelligent selection of a detachable bit to obtain optimum results requires careful consideration to achieve a balance between the three principal types of equipment used in the drilling process: 1—drill bits, 2—drill steel, and 3—drilling machines. Optimum results imply maximum output and minimum cost per unit of output. Since every rock type differs in drillability and it is generally impractical to provide equipment for more than one or two types of rock which may occur in one operation, selection of equipment must encompass average drilling conditions. However, on exceptional occasions several widely differing conditions may make it mandatory to provide equipment best suited to each condition. The choice of rock-drilling equipment is a most controversial subject and one that is further complicated by unreliable and frequently misleading performance claims. Small operators without the means for making accurate evaluations of equipment frequently suffer from these over-enthusiastic claims. It is apparent from experience in rock drilling throughout the world that rock drillability is not alike in any two places, and that selection of proper equipment can only be made after conducting thorough trials of various types of equipment. Some recent drilling tests in tactite and hornstone at the Darwin, California mine of the Anaconda Co. present some interesting clues on rock drillability. Microscopic examination of thin sections of these rocks reveals that mineral composition and rock texture are equally important in governing drillability. The Darwin hornstone is at times so abrasive that the carbide bit cutting edges become flattened to 3/32 in. in 2 to 4 ft of drilling, and some carbide bits were dulled to this point after 9 to 10 in. of drilling. This wear was determined to be the proper point for resharpening to eliminate carbide insert breakage or breakage of the steel rod when drilling with 1½ to 1?-in. bits, with a drifter of 2 3/4-in. diam and 90 to 100 psi air pressure, see Supplement A. Before considering the merits of various bit designs it may be well to review the mechanics of drilling rock with percussion drills. A sharp bit cuts by penetration and chipping. The amount of penetration governs the amount of chipping and depends upon the contact area of the cutting edge, the foot-

Jan 1, 1954

By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By P. G. Carpenter, H. B. Fisher, W. E. Bergman

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

The official Institute reports for the year 1929 were distributed in pamphlet form at the Annual Meeting, February, 1930, and were later included in Section 2 of Mining and Metallurgy, June, 1930, and thus made available to the entire membership. Membership In its report the Admissions Committee set forth the changes in membership during 1929, as follows: Total membership, Jan. 1, 1928, 8582; elected and placed on rolls in 1929, including 59 reinstatements, 509; loss by resignations in 1929, 88; loss by death in 1929, 110; loss by suspension in 1929, 37; membership at end of year not including Student Associates, 8856. Distribution of membership: Honorary Members, 16; Members, 6590; Junior Members, 38; Associates, 1041; Junior Associates, 1033; Rocky Mountain, 138; total membership, Jan. 1, 1930, 8856; Student Associates, 150; total including student associates, 9006. Treasurer's Annual Report, Year of 1929 Statement of Receipts For the year ended December 31, 1929 Dues: Arrears............................................ $ 3,501.75 Current............................................ 97,257.12 New Members...................................... 5,721.50 Advance........................................... 1,970.79 $108,451.16 Initiation Fees.................................................. 7,436.00 Magazine Receipts: Advertising Gross Receipts........................... $40,610.81 Magazine Sales..................................... 3,799.84 44,410.65 Sale of Transactions Current........................... $ 2,985. 15 Sale of Special Editions Current........................ 5,147.82 Sale of Back Transactions and Special Editions........... 4,186.93 Sale of Year Book..................................... 65.50 Sale of Authors' Reprints.............................. 2,585.40 Sale of Pins and Fobs.................................. 14.73 Sale of Technical Publications.......................... 1,451.55 Sale of Bindings...................................... 3,949.13 20,376.21 Net Interest Received: On Bank Balance and Temporary Investments......... $ 2,595.04 On Lie Membership Fund........................... 3,223.43 On James Douglas Library Fund...................... 5,425.61 On General Reserve Fund............................ 2,015.58 13,259.66 Miscellaneous Receipts........................................... 335.80 Total Receipts................................................ $194,269.48

Jan 1, 1930

By J. W. Edington

THE Hopkinson bar has become a popular technique for the measurement of the mechanical properties of materials deformed at high strain rate. Maximum use of the equipment is made in the arrangement first used by Kolskyl in which a short compression specimen is sandwiched between two pressure bars and is loaded by a single pulse travelling through the system. The pressure bars are used both to apply the load to the specimen and as transducers to obtain continuous strain-time histories of three pulses, incident on, reflected, and transmitted by the specimen. The data measured by the pressure bars can be analyzed in terms of the stress/strain behavior of the specimen.2'3 However, one of the assumptions of the analysis of the observed pulses is that the total stress and total strain do not vary significantly from point to point within the specimen at any given instant during the deformation process. Although this assumption is generally justified for very short disc-like specimens2 the situation is uncertain for larger specimens. For example, at small plastic strains (-0.01) Hauser et al.2 have some evidence of small flucations in the total stress within the crystal during deformation, even in relatively short aluminum specimens. In addition, Karnes4 has shown that the plastic strain, and by inference strain rate, is different at each end of a compression specimen tested in a Hopkinson bar, although the length of the specimen was not specified. Recently, the mechanical properties and the dislocation substructure have been investigated in single crystals of columbium5 (length 0.25 in., diam 0.19 in.), and copper6 (length 0.5 in., diam 0.5 in.) deformed at high strain rates. As part of this research program the assumption that the plastic strain is constant throughout the specimen has been checked by measuring the total dislocation density as a function of position in the specimen. Compression specimens of the same orientations and dimensions were tested as described previously5,6 sing a split Hopkinson bar. Since any discontinuity in strain distribution is most likely to arise during the initial stages of deformation the investigation was performed on specimens deformed to plastic shear strains of 0.054 (copper) at a strain rate 1.2 x l03 sec-1, and 0.06 (columbium) at a strain rate 1.5 X l03 sec-1. The orientation of the single crystals is shown in Figs. 1 and 3. Thin foils were taken parallel to the most highly stressed slip plane, i.e., (111) in copper and (011) in columbium, using conventional disc techniques. The dislocation densities were measured using first order reflections with compensation for invisible dislocations.5'6 In the copper single crystals the discs were randomly distributed throughout the cross section of the specimen. However, the dislocation density obtained from each disc was plotted vs the disc positions relative to the ends of the specimen. The results for the copper specimens are shown in Fig. 1. Clearly the dislocation density is constant throughout the main portion of specimen within the experimental error. The error bars on the dislocation densities correspond to a shear strain variation of 0.015 on the basis of previous measurements% ± of the rate of increase of dislocation density with strain in copper single crystals of the same geometry. Thus within this experimental error the plastic strain can be concluded to be constant within the specimen and the assumptions used in the analysis of the stress/time curves are therefore reasonably valid. The higher measured dslocation density near the impact end and the lower dislocation density at the bar end of the copper specimen is in agreement with the results of Karnes4 who showed that this strain/time curve rose to a maximum more rapidly at the impact end compared with the bar end. Hauser et al.2 have also pointed out that at small plastic strains (-0.01) the strain at the impact end of the specimen may be greater than that at the bar end. Thin foils taken from different points within the columbium single crystals demonstrated that the dislocation density could vary significantly within the specimen, see Fig. 2. Large areas of some thin foils up to 30 µ sq contained very few dislocations, see Fig. 2(a). However, in other parts of the compression specimen dislocation configurations like those shown in Fig. 2(b) existed over large areas (-30 µ sq). As a result, when the average dislocation density in a thin foil is plotted as a function of the position of the thin foil relative to the ends of the specimen, considerable scatter is observed, see Fig. 3. In this material then, the local dislocation density, and consequently the

Jan 1, 1970

By C. S. Giggins, F. S. Pettit

The oxidation of Ni-Cr alloys in 0.1 atm of oxygen has been studied at temperatures between 800" and 1200°C. For alloys with 30 wt pct or more Cr, continuous layers of Cr2O3 are formed during oxidation. In the case of alloys with chromium concentrations between approximately 5 to 30 wt pct, external scales of Cr203 are formed over grain boundaries whereas internal precipitates of Cr2O3 and external layers of NiO are formed at other areas on the alloy surface. When such conditions are present on the alloy surface, chromium diffuses laterally from those areas covered with a continuous layer of Cr2O3 to areas where a Cr2O3 sub scale exists and it is possible for the sub-scale zone to become separated from the alloy by a continuous layer of Cr2O3. Whether such a state will be attained depends upon the initial grain size of the alloy and the oxidation time. When the concentration of chromium in the alloy is less than 5 pct, Cr2O3 is formed internally both at grain boundaries and within the interior of grains and the alloy is covered with an external layer of NiO. MECHANISMS which describe the growth of oxide scales on nickel-base superalloys are complex and the effects produced by the various elements in these alloys on the oxidation behavior of superalloys are not clearly understood. In order to determine the influence of the different elements on the oxidation behavior of superalloys, it is first necessary to examine the oxidation properties of binary nickel-base systems which contain the principal elements present in the superalloys and then progressively more complex systems until compositions typical of the superalloys are attained. Chromium is present in virtually all nickel-base superalloys and the purpose of the present studies was to examine the selective oxidation of chromium in Ni-Cr alloys. The oxidation characteristics of Ni-Cr alloys have been extensively studied1-" to date principally as a result of the high oxidation resistance exhibited by some of these alloys. Ni-20Cr* has long been known *All compositions are given as wcight percent unless specified otherwise. to be oxidation resistant and is commonly used as resistance heating elements for service temperatures up to 1100°C. This alloy cannot be used for extended periods of time at higher temperatures because of the apparent reaction of the external scale with oxygen to form gaseous CrO3. In spite of the considerable work cited above some important aspects of Ni-Cr oxidation still remain unresolved. Virtually all of the previous studies agree that small additions of chromium to nickel, e.g., <10 wt pct Cr, result in increased oxidation rates as compared to that of pure nickel, whereas larger additions, e.g., 20 to 30 wt pct Cr, form alloys with substantially lower oxidation rates. The controversial aspects of the oxidation mechanisms for these alloys that still remain unresolved are as follows: 1) A description of the oxidation mechanism for the low chromium alloys. 2) A description of the oxidation mechanism for the high chromium alloys, particularly with respect to the composition of the external scale which results in the lower oxidation rates. 3) The specific alloy compositions at which the oxidation mechanism changes from that obtained for low chromium contents to that of the high chromium alloys and the reason for this transition. EXPERIMENTAL The Ni-Cr alloys listed in Table I were prepared from high purity metals by nonconsumably arc melting and casting as buttons. These alloys were then given a preliminary annealing treatment in argon at 815°C for 100 hr to promote homogeneity. Each button was cut into 0.250 in. thick sections that were subsequently cold-rolled to 0.050 in. thicknesses and annealed in argon at 815°C for 48 hr to provide a twinned, equi-axed grain structure. The grain size for these alloys was not uniform and the limits, within which the average grain size lies, are given in Table I for the single-phase alloys. All the alloys were single phase with the exception of the Ni4OCr alloy in agreement with the Ni-Cr phase diagram.&apos;&apos; Rectangular specimens were cut from the sheet to provide surface areas of approximately 2.5 sq cm. Exact areas were determined with a micrometer after surface preparation was completed. All of the specimens except the Ni-40Cr alloy and pure chromium were polished through 600-grit Sic abrasive paper, ultrasonically agitated in ethylene trichloride, rinsed with ethyl alcohol, and electro-polished. The specimens were electropolished in a 10 vol pct H2SO4 (conc), 6 vol pct lactic acid, methyl alcohol solution at 70" to 80°C for 2 min at a current density of 0.8 to 1.2 amp per sq cm. This electro-polishing procedure did not produce acceptable surfaces on the Ni-40Cr alloy nor on pure chromium and the oxidation properties of these materials were obtained for specimens polished through 600-grit Sic

Jan 1, 1970

By V. Leroy, A. G. Guy

Serious disagreements are often found between experimentally determined intrinsic diffusion coefficients and those calculated employing the usual form of the vacancy theory. In the new theory it is proposed that the total intrinsic flux, Ji, of component i, is the sum of a part, f, due to the usual random exclzanges of component i with the vacancies, and a second part, Ji, due to exchanges with the uacancies composing the net vacancy flux. The present treatment, while less powerful than that of Manning, has the advantage of easy uisualization and of facilitating the application of the vacancy-flux effect to complex systems. IT is becoming increasingly evident that there are serious deficiencies in the version of the vacancy theory of diffusion that has been widely used for the past 20 years. One type of evidence is the frequent lack of agreement between intrinsic diffusion coefficients and tracer diffusion coefficients, even taking account of the thermodynamic factor. A second kind of evidence is the observation of a Kirkendall shift larger than theoretically possible, that is, larger than can be accounted for without assigning a negative value to one of the two intrinsic diffusion coefficient.&apos;- The thermodynamic factor could conceivably make both coefficients negative, but not just one. It is clear that a cause of these anomalies, apart from any inadequacy of the usual vacancy theory, might lie in an oversimplified treatment of the data. Adequate experimental techniques, including the use of moderate pressure during the diffusion anneal, are now available to insure that porosity, lateral expansion, and so forth, can be kept negligibly small in most cases. The effect of differences in atomic volume can be of major importance, and it is essential that one of the available methods4 be used to account for this factor. In the present treatment this is accomplished by the consistent use of moles per cubic centimeter as the unit of concentration. Of the various possible inadequacies of the vacancy theory, attention will be given here only to effects of the net vacancy flux. annin&apos; has previously considered this question, beginning with an analysis of atomic jumping of tracer atoms. When he added the effect of a concentration gradient, new terms arose that could be associated with the flow of vacancies. The present treatment uses quite a different approach. The usual vacancy flux, J,, is introduced explicitly, and a simple analysis predicts major changes in the intrinsic diffusion coefficients from this cause. The usual assumptions are made that only a vacancy mechanism is operative, that the formation of voids can be neglected, and that changes in the partial molal volumes, vl and v2, are negligible. The significant diffusion coefficients for the present topic are Dl and D,, the intrinsic coefficients, which enter in the equations, where the flux Ji, moles per sq cm per sec, is that crossing the Kirkendall interface. The concentration, ci, is in units of moles per cu cm, and the concentration gradient, aci/ax, is evaluated at the Kirkendall interface. It will be recalled&apos; that the calculation of Dl and D2 involves the measurement of areas on the diffusion curve with respect to the positions of the Kirkendall and Matano interfaces. In the case of the anomalies mentioned earlier, the Kirkendall shift is too large to be accounted for by the diiferetzce in fluxes (J2 -J1), given by Eqs. [I] and [2]. The logical inference is that the flux of the solvent atoms, J1, is actually in the same direction as the flux of the solute atoms, Jz. In terms of Eq. [I] this requires that Dl have a negative value. However, it would be somewhat misleading to state that the solvent atoms are diffusing up their own concentration gradient. The explanation that will be advanced here pictures competing processes producing the net flux of solvent atoms: 1) diffusion of the solvent atoms down their own gradient by random exchanges with vacancies; and 2) diffusion of solvent atoms in the opposite direction by exchanges with the net vacancy flux. ACTION OF THE NET VACANCY FLUX Theories of vacancy diffusion can be formulated with varying degrees of refinement, and the present theory has purposely been kept as simple as appeared adequate to explain the phenomenon in question. In particular the following aspects have been neglected: 1) the gradient of vacancy concentration in comparison to the gradient of the atomic species; 2) departure of vacancy concentration from the local equilibrium value; 3) variation of the jump frequency, LO, with the specific surroundings of the atom-vacancy pair being considered; 4) correlation effects. These and other refinements can be considered once the essential mechanism has been established. The essential idea of the present analysis is to calculate the total intrinsic flux, Ji, of component i as the sum, JlJ?±j{ [3] where J; is attributable to the usual random atomic jumping, and J{ is a contribution arising from the net vacancy flux, J,. The latter quantity, of course,

Jan 1, 1967

By Amitava Gangulee

A recent investigation has shown that solid solution hardening is almost absent in the quasibinary system SnTe-pbTe.1 The lack of solid solution hardening was attributed to the small difference of only about 3 pct between the atomic sizes of lead and tin, and to the fact that the formation of these solid solutions involved changes only in the sublattice occupied by the lead and tin atoms. The investigation reported here is concerned with the quasibinary system PbSe-PbTe which, similar to the SnTe-PbTe system, forms a continuous series of solid solutions2 and has the same NaC1-type (Bl) structure. The size difference between the selenium and tellurium atoms, however, is slightly larger than 7 pct. No indication of any ordering of the lead and tin atoms at. selected compositions had been found in the system SnTe-PbTe, which had been explained by the weak second-nearest-neighbor interactions between lead and tin atoms.&apos; The possible occurrence of an ordering transition in the system PbSe-PbTe was also investigated in the present work. Polycrystalline specinlens of PbSel-1-xTex (x = 0, 0.20, 0.25, 0.33, 0.50, 0.67, 0.75, 0.80, and 1.0) were prepared by melting appropriate amounts of 99.999 pct pure Pb, Se, and Te j.n evacuated and sealed Vycor capsules. The capsules were quenched in water. The solidified ingots were homogenized at 800°C for 14 days. Chemical analysis of the homogenized ingots showed that the deviations from the stoichiometric compositions were less than 0.1 at. pct for each component. Part of each ingot was ground to pass through a 75 g sieve and pressed into 25.4 mm by 12.7 by 2 mm briquettes. Duplicate sets of specimens, each containing at least one briquette and part of the ingot of each composition, were sealed in evacuated Vycor capsules. Both sets were annealed at 500°C for 7 days; one set was quenced in ice-water and the other was cooled to room temperature over a period of 14 days.

Jan 1, 1970