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By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By T. R. Armstrong

Total crude oil production in Mexico in the year 1941 is estimated at approxi- mately 41,000,000 bbl.; a daily average of 112,700 bbl. and a decrease of about 5 per cent as compared with the daily average of 120,000 bbl. produced in the year 1940, and nearly 11 per cent decrease as com-

Jan 1, 1942

By Lewis M. Haupt

Discussion of the paper of Mr. Granger, presented at the New Haven meeting, February, 1909, and published in Bulletin No. 25, January, 1909, pp. 1 to 37. LEWIS M. HAUPT, Philadelphia, Pa. (communication to the 'Secretary*) :-This subject is of great interest to me, and I am noting progress and conditions as a test of my own judgment in advocating what I believed to be the nearer, cheaper and better route at Nicaraugua. I have as yet learned nothing to change my views, or modify the convictions which led me to retire from the Commission; but that is not the issue to-day. Our government is committed to the Panama route, and is bound to " make good." There are many points presented by Mr. Granger which seem to me worthy of very serious consideration. But when all is said there remains the risk of seismic convulsions, to which either form of canal is subject; and I fail to see that the risk would be reduced by making the cut deeper, with greater surcharge of lateral pressure upon the side walls. A severe earthquake in the rainy season would doubtless close either type of canal. One of the arguments in favor of the Panama route most insisted on, was that Nature had provided good natural harbors at its termini. Recalling this, it has interested me to note that the cost of creating the necessary harbors is estimated at $27,000,000. Mr. Granger refers to this, and quotes the Board's report to the effect that, on the Atlantic side, it will require 5 miles of jetties to " make an excellent harbor out of a wretched one." The vulnerable part of Mr. Granger's paper seems to me to lie in the admission that the plant required is still in the embryonic stage, and that at least one machine should be built and tested " to demonstrate that the theoretical strains and forces work out in practice exactly as expected." This, how-

Jul 1, 1909

By R. P. Alger, M. P. Tixier, D. R. Tanguy

In the combination induction-electrical log used at present in the field, the induction logging tool is appropriate for the investigation of moderately invaded formations. A new induction sonde with a radius and investigation about twice as large has been developed recently for the case of deep invasion. It has very nearly the same vertical resolution as the present sonde so that thin beds are defined as accurately as before. The characteristics of the new tool are described, the corresponding interpretation charts are given and field examples are discussed. The design of the sonic logging tool has been modified to improve the calibration and the reliability. The fact that porosity can be accurately recorded by means of the sonic log has prompted new interpretation procedures for saturation estimation, wherein the data concerning the various permeable beds in a given well are correlated. One approach consists of plotting transit time vs true resistivity, with an appropriate scale. With this approach, saturations can be estimated conveniently even in cases where formation water resistivity is not well known. In another approach, a comparison is made of the values of the formation waters computed from the re- sistivity and sonic logs. Using the concept of continuity, this procedure makes possible a quick determination of zones of saturation in shaly sands and/or in case of appreciable variations of formation salinities with depth. It has been found that the comparison of porosity from the sonic log with the apparent porosity computed from a short-investigation resistivity log may reveal, in many cases, the presence of residual oil and thus detect potentially productive formations; this procedure is valuable when the true formation resistivity and the resistivity of the formation water are in doubt. INTRODUCTION During the past year, the efficiency of log interpretation has been vastly improved. The improvements have largely resulted from the introduction of a deep-investigation induction device and from the application of new interpretation techniques that utilize sonic vs resistivity readings. Since the new interpretation techniques depend, in part, upon good values of true formation resistivity, the new induction log will be discussed under Part I. The sonic interpretation techniques will be studied under Part 11. Early in 1959, the 6FF40 induction equipment was introduced in the field. This device was designed for a better approach to true formation resistivities in deeply invaded zones. The greatly improved radial investigation of the 6FF40 equipment has been achieved without sacrificing vertical resolution. The first combination induction-electrical log, the 5FF40, was introduced as a standard tool in 1956 for the logging of wells drilled with fresh muds. The tool has received wide industry acceptance in the United States. 'The 5FF40 induction log has a radial investigation sufficient to overcome average depths of mud filtrate invasion. At 5d invasion, for example, the 5FF40 induction log will read about 1.4 R. in a water sand where R., = 10R,. At 10d invasion, such induction log would read 2.45 R. in the same water sand. In either case, the effects of invasion would not be sufficiently great to cause a water sand to be mistaken for a shale-free oil- or gas-producing zone. Some formations, however, invade deeply — in excess of 10d. Such water zones could be mistaken for oil-or gas-saturated sands unless the porosity balance' can clearly make the distinction. It is for these deeply invaded formations that the 6FF40 was developed. CHARACTERISTICS OF THE 6FF40 Radial Investigation Characteristics To describe the comparative responses of the 5FF40

By R. V. Sara

Determination of the Hf-C phase diagram was conducted primarily by metallographic and X-ray diffraction studies on appropriate alloys. The only intermediate phase observed in this binary system was HfC. This phase was found to be homogeneous between 34.0 and 48.0 at. pct C at 2200°c and between 36.0 and 49.3 at. pct C at 3150°C. The lattice-parameter variation was also determined for HfCI-, compositions prepared at 2200° and 3150°C. The most most refractory composition, with a melting point of 3830°c, was established at 47.5 at. pct C from melting-point data. Solidus temperatures of 2240' and 3150°C occur on the high-kafnium and high-carbon sides of the monocarbide, respectively. The invariant point between HfC and carbon is located at 66.0 at. pct C, whereas the 2240°C solidus corresponds to the peritectic temperature at which hafnium is formed from HfC and hafnium-rick liquid. Hafnium has a melting temperature of 2208°C and is capable of taking carbon into solution to the extent of 10.5 at. pct at this temperature. ALTHOUGH the Hf-C phase diagram has not been previously evaluated experimentally in its entirety, the belief has been that the general configuration would resemble the chemically similar Group rV carbide systems, Ti-C and Zr-c.' These binaries are characterized by a single carbide phase with a simple NaC1-type structure which is maintained over wide compositional ranges. This family of carbides has high thermal stability that increases substantially as the atomic number of the metal component increases. This trend characterizes HfC as one of the highest melting materials. According to Agte and Alterthum,2 the melting point for this monocarbide is 3890°C, a value that has been quoted quite extensively for the past several decades. Recently, in repeating the work of Agte and Alter-thum, Adams and Beall3 determined the melting point of HfC to be 3895°C. A significant departure from the commonly accepted version of the Hf-C system was reported by Avarbe and his coworkers,4 who proposed that there is an extreme stabilization of a hafnium in a narrow field to 2820°C, above which it melts peritectically to form HfC and liquid. Their study was also concerned with the melting temperature of various HfCI-, compositions, but the peak melting point was taken from the work of Agte and Alterthum. Avarbe and his associates were not concerned with the high-carbon region of the system. However, three widely varying temperatures have been reported for the HfC-C solidus by other investigators. Cotter and Kohn5 observed approximately 2800°C; Portnoy et al.' reported 3260°C; and, more recently, Krikorian7 indicated 2915°C. Equally as uncertain is the solidus between hafnium and HfC. As noted above, Avarbe et al. report a peritectic temperature of 2820°C, Krikorian7 measured 2150°C, and Benesovsky and Rudy' estimated 2000°C on their diagram. I) EXPERIMENTAL PROCEDURE The starting materials for this study consisted of reactor-grade hafnium hydride obtained from Fair-mount Chemical Co., Newark, N.J., hafnium carbide supplied by Wah Chang Corp., Albany, Ore., and Union Carbide spectroscopic-grade graphite, SP-1. The graphite analysis indicated impurities at levels of only 0.5 ppm or less. According to the suppliers, the hydride and carbide contained the typical impurities listed in Table I. The samples required for these studies were prepared by dry blending either graphite and hafnium hydride or hafnium hydride and hafnium carbide powders for approximately 5 min in a "Spex Mixer Mill". The latter combination was used only for preparing several samples in the HfC1-, melting-point studies. Small pellets, varying between 3/16

Jan 1, 1965

By P. F. Gnirk, J. B. Cheatham

Single bit-tooth penetration experiments under static load were conducted on six rocks at confining pressures of O to 5,000 psi using sharp wedge-shaped teeth with included angles ranging from 30 to 120° In general, the force-displacement curves for all rocks exhibit an increasingly nonlinear and discontinuous behavior with decreasing confining pressure. The confining pressure at which a rock exhibits a macroscopic transition from predominantly ductile to predominantly brittle behavior during penetration vmies from about 500 to 1,000 psi for the limestones to greater than 5,000 psi for dolomite. The correlation between calculated values of force per unit penetration based on plasticity theory and experimental values is quite encouraging, even at confining pressures as low as 1,000 psi A qualitative correlation between volume of fragmented rock per unit energy input for a single bit-tooth and drilling rate for microbits appears to exist over a confining pressure range of 0 to 5,000 psi. INTRODUCTION Laboratory experiments utilizing a small-scale drilling apparatus have demonstrated that penetration rates are reduced considerably as a result of increasing the confining pressure from atmospheric to a few thousand psi?-3 This undesirable situation can, in general, be attributed to a combination of decreased efficiency of chip removal at the bottom of the borehole, increased rock-failure strength, and a possible change in the mechanism of chip generation and rock fragmentation with increasing confining pressure. To more fully understand the principles underlying the last circumstance, it is the purpose of this investigation to experimentally study the mechanism of single bit-tooth penetration into dry rock at low confining pressures and, in particular, to establish the confining pressure at which the penetration mechanism may undergo a brittle to ductile transition for various rock types commonly encountered in drilling. Confining pressure as used here refers to the differential pressure between the borehole fluid pressure and the formation-pore fluid pressure. EXPERIMENTAL PROCEDURE Using an experimental apparatus previously described: a single, sharp wedge-shaped tool was forced under a "statically" applied load into an effectively semi-in finite dry rock sample subjected to a prescribed confining pressure. To prevent the invasion of the con fining-pressure fluid into the pores of the rock sample during penetration, the exposed surface of the rock was jacketed with a layer of silicon putty.* Electrical instrumentation incorporated into the apparatus yielded a graphical plot of force on the tool as a function of penetration or displacement of the tool into the rock during an experiment. During the course of the experimentation the following conditions were maintained constant: (1) pore pressure — atmospheric (i.e., the rock was dry); (2) temperature — 75F; (3) rate of loading — essentially static (approximately 0.002 in./sec); (4) bit tooth — a sharp wedge-shaped tool loaded normal to the rock surface; (5) rock surface — smooth and flat; (6) drilling fluid — hydraulic oil; and (7) maximum depth of penetration — approximateiy 0.1 in. In addition, each experiment was performed on a different rock sample so the rock surface is free of a layer of cuttings and of any previous indentation craters. The influence of the corners of a borehole was neglected, since each rock sample was cemented inta a section of aLuminum tubing to simulate a semi-infinite body. Indentation experiments were made on a sandstone, two limestones, a marble, a dolomite and a schist with a 60' bit-tooth over a range of confining pressures from atmospheric to 5,000 psi and at a constant confining pressure of 1,000 psi for a variety of bit-teeth with angles ranging from 30 to

Jan 1, 1966

By J. L. Giove, J. M. Hodge, R. G. Storm

The hardenability effect of molybdenum has been evaluated by a number of investigators, including one of the present authors.1,2,3,4,6 Considerable discreMncy exists, however, among the results of these various investigators, and two of them, Brophy3 and Kramer,4 have indicated that the apparent hardenability effect of molybdenun would vary, depending upon the other alloying elements in the steels being considered. The results of previous, unpublished work conducted at the Duquesne Works Laboratory of the Carnegie-Illinois Steel Corporation also have indicated significant differences in the hardenability effect of molybdenu~n in nickel and in chromium steels. The present investigation was undertaken in an effort to establish the mechanism governing this difference in the hardenability effect of molybdenum. This work involved both end-quench hardenability and isothermal transformation tests on two series of steels of varying molybdenum content. One steel contained 3 pct nickel and the other 1 pct chromium. It was hoped that such studies would shed further light on the mechanism of this behavior. Materials and Experimental Work MATERIALS The chemical compositions of the steels used in this investigation arc shown in Table 1. These steels were furnished by Battelle Memorial Institutc in the form of 100-lb induction furnace ingots. The top half of each ingot was forged to 1 3/8-in. square billets and then rolled to I-in. round bar stock for isothermal transforma- tion studies. The bottom half of each ingot was forged into approximately 1 1/4-in. rounds for end quench tests. All of the steels were normalized from 1650°F and tempered at 1100°F before nlachming to end quench or isothermal samples. END-QUENCH TESTS standard l-in. diam end-quench tests were made on each of the steels. The test bars were austenitized at 1600°F for 30 min,, quenched in a standard Jominy jig, and hardness surveys were made in all tests. The 95 pct martensite point was deterInined from hardness values5 and cheeked by metallographic examination. The jominy distance values for 95 pct martensite were converted to hardellability values in terms of ideal diameter (Dl), using a revised carve for the relationship between Jominy distance and ideal diameter. This curve was based on the cooling time from the A1 to the bainite nose temperatures rather than on the usual criterion of half-temperature time. The cooling rates as determined by Russell and Williamson9 were used as a basis for this relationship. The derivation of this curve is described in detail in the appendix. ISOTHERMAL TRANSFORMATION STUDIES Samples for the isothermal transformation studies were quarter sectors of 1/16.is-in. thick slices from the 1-in. round bars. All samples were austenitized for a total the of 15 min., transferred rapidly to a lead bath for isothermal transformation, and brine quenched from the lead bath. A time of 3 see was allowed for the sample to come to the temperature of the lead bath, and this time was not included in the isothermal transformation times. Each sample was examined metallo-graphically at a magnification of 100 diam. The per cent transformation was estimated by comparison with standard micrographs, and the values were plotted against the on log/log coordinate paper. At least 4 and as Inany as 10. points were plotted for each steel. A line was drawn through the points for each steel, and the times for 5 pct transformation were obtained from the plot for each steel. Isothermal transformation diagrams in terms of 5 pet total transformation, covering the temperature range of 800 to 1200°F, were determined in this manner for an austenitizing temperature of 1600°F. The times for 5 pct transformation at the bainite nose for austenitizing temperatures of 1800 and 2000°F were also determined in the same manner. These times for 5 pct total transfor-

Jan 1, 1950

By G. R. Speich, D. J. Mack

The transformation of was studied by isothermal methods. At all temperatures, the ß transforms quickly to fine grained ß" which develops silver-rich striations. At higher temperatures the striations disappear, the final structure being Widmanstatten a in ß'. At lower temperatures, the striated ß" is consumed by pearlite nodules of a + ß' which in turn form the Widmanstatten a in ß'. The transformation is unlike any previously reported for a eutectoid. AS part of a general program of study on the eutectoid reaction, the Ag-Cd eutectoid seemed particularly attractive because the ß phase which undergoes the reaction is another of the typical "electron compounds," AgCd, having the disordered body-centered cubic structure. This work deals with the eutectoid which occurs at 50.5 wt pct Ag, and not with the eutectoid which has been reported at 42.9 pct Ag.' There has been no work reported specifically on the Ag-Cd eutectoid which was studied. The only information available on this eutectoid is that work done in the determination of the phase diagram. For the most part, the terminal portions of the diagram, Fig. 1, are well established; however, the region from 40 to 60 pct Cd is still somewhat in doubt. The X-ray evidence'..' in this region is in conflict with the results of thermal analysis. X-ray analysis3 does not show a polymorphic transformation at about 240°C as indicated by thermal analysis.1,5 Even the X-ray evidence, within itself, is confusing in this region of the diagram. One investigator2 reports the ß phase as hexagonal close-packed and has found three phases in the one-phase ß field. Other X-ray investigators"' ' report the ß phase as body-centered cubic. The authors believe that much of the confusion resulted from incomplete homogenization of the alloys. It was found that it takes almost a week to produce a completely homogeneous two-phase structure at 370°C. Another possible source of error is the volatilization of cadmium from the surface and cracks of the specimen during annealing with the possible formation of a cadmium-poor phase. The only metallographic data available on this eutectoid alloy are those of Durrant1 and Fraenkel and Wolff.5 his information is very limited. The phase diagram chosen as most nearly correct is that in the Metals Handbook," which is almost identical with the phase diagram suggested by Durrant.1 Materials and Procedure The alloy was prepared from high purity silver (999.5 plus fine) and high purity cadmium (0.02 Pb, 0.005 Cu, trace Fe). The metals were melted in carbon under a nitrogen atmosphere. Some cadmium was lost by volatilization but by remelting several times and adding cadmium a 200 g ingot of approximately eutectoid composition was obtained. Because the CdO fumes are quite toxic, the exit gas from the furnace was led through a water trap to condense the CdO. The ingot was homogenized at 650°C for 24 hr, no attempt was made to prevent decadmiumization. This resulted in a narrow decadmiumized rim on the ingot which was removed. Filings for analysis were obtained from cross sections of the ingot. Silver was determined by the Volhard thiocyanate method,? cadmium by difference. The ingot analyzed 50.8 pct Ag at the top of the ingot and 50.7 pct at the middle and at the bottom of the ingot. This alloy was only slightly hypo-eutectoid compared to the accepted value of 50.5 pct Ag and was used for the isothermal studies. It was felt that further attempts to adjust the composition might be futile because of the volatility of the cadmium. The ingot was sectioned to specimens approximately 3/4 x 3/4 x 1/8 in. These specimens were "austeni-tized" for 3 hr in air at 650°C to yield homogeneous ß and then quenched into a salt bath held at constant subeutectoid temperatures where the transformation

Jan 1, 1954

By J. T. McGrath, R. C. A. Thurston

Poly crystalline specimens of copper, and copper with various additions of zinc, were tested in plane-bending fatigue. In tests performed at a constant stress, the fatigue life of copper increased slightly with the addition of up to fifteen per cent zinc. There was a sharp increase in fatigue life as further additions of zinc of up to 35 pct were made. Surface observations showed that the coarse slip bands that are characteristic of fatigue became narrower as the concentration of zinc increased. The rate of crack propagation also decreased with increasing zinc content. It is suggested that the fatigue behavior is controlled by cross slip processes. CROSS slip occurs when dislocations move from one primary slip plane to another along a connecting or cross slip plane. The primary and cross slip planes have a common slip direction. Wide stacking faults, having low energy, tend to make cross slip more difficult. According to recent theories, the ability of a material to cross slip is important to the formation and propagation of fatigue cracks. McEvily and Machlin2 have examined this concept experimentally by fatiguing single crys tals of lithium fluoride, sodium chloride, silver chloride, and KRS-5.* The latter two materials ex- hibit easy cross slip, while the former two do not. Normal rapid fatigue failure was obtained in the silver chloride and KRS-5 specimens, whereas it was much more difficult to achieve in sodium chloride and lithium fluoride crystals. Furthermore, numerous slip band extrusions and intrusions were found in silver chloride and KRS-5 crystals, whereas only one isolated extrusion was found in lithium fluoride and none was found in sodium chloride. McEvily and Machlin also consider that there is no clear-cut demarcation between crack initiation and propagation. The intrusion-extrusion process, which initiates crack formation, continues ahead of the cracks to allow propagation of these cracks along slip bands. The process of cross slip is therefore important not only to crack initiation, but also to crack propagation. Holden4 postulates that fatigue crack growth is dependent upon cross slip and thus upon stacking-fault energy. Using an X-ray microbeam technique, he found a cyclic subgrain structure in fatigued aluminum and a-iron. Holden suggests that micro-cracks develop in the densely-packed sub-boundaries ahead of the main crack front, and when sufficiently numerous join up to promote crack growth. The ease with which a subgrain structure could form would depend upon the ability of the dislocations to cross slip, and thus upon the stacking-fault energy. Hence in aluminum, which has a high stack-ing-fault energy and in which cross slip is easy, Holden found that the relative rate of fatigue crack propagation was considerably greater than in stainless steel, a low stacking-fault energy material. It has been shown by a number of investigators that the probability of forming deformation stacking faults in copper increases as zinc is added.5-7 Cross slip should, therefore, become more difficult as the zinc concentration is increased. In order to check the validity of the foregoing theories, it was decided to test copper and copper with various additions of zinc in plane bending fatigue, and determine to what extent their fatigue properties are dependent upon their ability to cross slip. EXPERIMENTAL PROCEDURE Fatigue tests were carried out on polycrystalline OFHC copper and various copper-zinc alloys with 5, 15, 20, 30, and 35 wt pct Zn. The Cu-Zn alloys were obtained commercially in sheet form. Test specimens, as shown in Fig. 1, were machined from sheet that had been reduced to an approximate grain size of 0.040 mm, the heat-treatment procedure being similar to that of Feltham anc copley.8

Jan 1, 1963

By J. Kostuik, M. J. de Bastiani

The method of mining the uranium orebody at Denison mine in the Elliot Lake district of Ontario is discussed. Details of the development of haulage-ways and rooms are giuen, as well as methods of ore haulage. The milling and beneficiation stages are noted briefly. Located in the Elliot Lake mining district of Canada, the Denison mine lies between Sudbury to the east and Sault Ste. Marie to the west, Fig. 1. This area is overlain by Huronian sediments filling a basin in the Keewatin basement complex. Subsequent folding of these sediments developed a synclinal structure, known locally as the Quirke Lake Trough, which forms the northern portion of the now famous big Z structure, the geological trademark of this region. Plunging to the west and extending nine miles from the granite outcropping in the north to the Keewatin lava contact to the south, the syncline has dips of 10" to 45" on the north limb and 10" to 20" on the south limb, Fig. 2. The Denison orebody, located on the north limb of the syncline, lies between 800 and 3000 ft below the surface. The main ore zone is within 50 ft of the Missisagi-Keewatin contact (see Fig. 3), and it varies in thickness from 6 to 32 ft. This ore zone has a composite dip of 19" to the south and is composed primarily of two pyritized conglomerate beds separated by a band of pebbly quartzite stratum. The upper conglomerate bed of the main zone varies from 2 to 15 ft in thickness, while the lower conglomerate varies from 2 to 12 ft. Over extended areas, mining is carried out over the entire section comprising the two conglomerate layers and intercalated quartzite; in other areas, the conglomerates are selectively mined, depending on the thickness of the quartz-ite. The ore zone contains approximately 6 pct sulfides and 80 pct silica. The predominant uranium-bear ing minerals are brannerite, uraninite, and an unidentified mineral (probably thucolite). Some of the uneconomic metallic minerals identified to date are pyrite, pyrrhotite, and chalcopyrite. MINE LAYOUT Shafts: Underground exploration and development (Fig. 4) were performed through two shafts 1/2 mile apart. The No. 1 shaft, sunk to a depth of 1856 ft with the main station established at the 1600-ft ore level, is a 250-sq ft, 5-compartment shaft capable of handling 4500 tpd. Two 5x5-1/2-ft compartments serviced by a 12-ft diam double-drum hoist, are used for hoisting 190-cu-ft bottom-dump skips in balance. A 30-man cage, offset by a counterbalance, operates within a 5-1/2x11-1/2-ft compartment. The fifth compartment is used as a manway, pipe, and cable-way. This shaft is also provided with an intermediate pumping station used during the initial mining phase as well as loading-pocket and spill-pocket installations and pumping facilities. The 480-sq ft No. 2 shaft, located down-dip from No. 1 shaft, has a 2776-ft depth. Serving as the main hoisting shaft with a maximum capacity of 9000 tpd, it has eight compartments, four of which are used for hoisting ore in 10-ton capacity bottom-dump skips. These four compartments, measuring 5x6-ft in section, are serviced by two 12-ft diam double-drum semi-automatic hoists. A 50-man cage is operated in a 15x8-ft compartment, and it is counterbalanced by a 12-ton weight. Two compartments are used for ventilation, manway, electric cables, and pipes. A station was constructed at the 1325-ft horizon of the No. 2 shaft for relay pumping. The main sta-

Jan 1, 1961

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.' The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

By J. R. Dawson, J. A. Glunt

VESTA No. 4 and 5 mines supply most of the high volatile coal required for Jones & Laughlin's byproduct coke plants. Until 1944 all coal produced in these mines was loaded by hand. Pressure to mechanize at Vesta was brought on by the manpower shortage in World War 11, and in 1943 a decision was made to change to mechanical loading. It was the opinion of those concerned that by use of selective mining the coal would be clean enough to be processed by the existing preparation plants. At that time coal cleaning at Jones & Laughlin consisted of hand picking the larger sizes at the mine tipples and wet washing at plants located at the Pittsburgh and Aliquippa Works. A typical section of the Pittsburgh seam as it occurs at Vesta is shown in Fig. 1. The 14 to 16 in. of drawslate immediately over the coal is too soft to be used for roof and must be taken down, leaving the rooster coal just above for roof. In selective mining an attempt is made to mine the coal under the drawslate first and then load out the drawslate separately as refuse. In full seam mining slate and coal are shot down at the same time and loaded out. Mechanical loading at Vesta created new problems. It was found that selective mining, even when carefully applied, increased the refuse in the raw coal to such an extent that the washers at the mills were unable to handle it. Large tonnages of refuse were being transported, a reject disposal problem was created, and good metallurgical coal was being loaded out and lost. In addition, the selective method handicapped operation of the loading machines. Fig. 2 shows how the ash content of the raw coal increased as mechanization proceeded at No. 5 mine. New Preparation Plant: After an exhaustive study of this situation by J & L management, is was decided that a preparation plant should be constructed at the mines, capable of handling full seam mined coal and large enough to process full production of both No. 4 and No. 5 mines. It was decided that from the standpoint of inside operation and haulage the new plant should be located as near as possible to the old No. 5 tipple on the Monongahela River near Vestaburg. Full seam mining at Vesta could be expected to produce a tremendous volume of refuse along with the coal, since 14 to 16 in. of slate would be mined with an average 78 in. of coal. Disposal of this refuse required serious consideration in selecting a plant site. The only area near Vestaburg large enough for disposal of the plant refuse was across the Monongahela River at LaBelle. Ample space was available here, and construction at this location would not interfere with operation at the No. 5 tipple. It had been noted over the years that the sulfur content of the coal produced at Vesta was gradually increasing, and there was every indication that this increase could be expected to continue as the mines developed further from the river. It was decided to construct a three-part separation plant with complete blending facilities to produce both metallurgical and steam coal. In this system an attempt is made to reduce the sulfur in the metallurgical coal in a secondary cleaning process. Construction of the new preparation plant got under way early in 1947 and continued until the spring of 1950. The plant was designed to handle 2400 tph of raw coal containing 30 to 35 pct refuse. Cost of outside buildings and equipment was about $14 million. Total cost of the plant, together with improvements and changes made at this time, was approximately $21 million.

Jan 1, 1957

By Robert K. Waits

The resistivity, temperature coefficient of resistance, stability at 200°C, and structure of annealed Si-Cr films have been studied as a function of film cowposition. Colorimetric analyses of the films indicated 20 to 60 wt pct Cr over the resistivity range of 1 to 10-4 ohm-cm. Resistors were delinealed by photolithographic etching, contacted with aluminum, and mounted in TO-5 packages. The average temperature coefjicient of resistance, a, between 50" and 150°C is related empirically to the film resistivity, p, by a (ppm per °C) = -2900 - 1140 log p (ohm-cm). Near a resistivity of 3.5 x 10-3 ohm-ctn (30 at. pct Cr) , the temperature coefficient changes from positive to negative. The temperature at which the resistance maximum occurs increases with decreasing resistivity. The conduction mechanism between —196" and +360 C appears to have two components—an activated conduction dominating a1 lord chromium content and higher temperatures and a linearly temperature-dependent conduction dominating at high chromium content and low temperatures. Electron diffraction patterns showed the films to consist of Cr3Si and amorphous silicon. Resistors thicker than 150A typically drifted less than 0.6 pct after 5000 hr stor-age at 200°C. Resistors as thin as approxinzately 80°A that had a silicon overlayer showed similar stability. Such films had sheet resistivities of 10 kilohm per square and temperature coefficients near —600 ppm per "c. THIN-FILM resistors having sheet resistivities greater than 1 kilohm per square are required in many integrated circuit applications. A process for producing such resistors should be compatible with present circuit fabrication and packaging, including exposure to maximum temperatures of 300° to 570°C during contact alloying, die-attach, and ceramic package sealing. In addition, the resistors should have a low temperature coefficient of resistance and change less than 1 pct during storage at temperatures up to 200°C for 1000 hr or longer. Reports of work beginning in 1949 at Battelle Memorial Institute indicated that, among other materials, the silicides of chromium, Cr-Co, molybdenum, tantalum, and tungsten were worthy of further study as high-stability resistive films. Later work on Si-Cr films vacuum-deposited by flash evaporation from a tungsten boat1 led to the conclusion that Si-Cr had "excellent properties for development into high- stability ... resistive elements". More recently, Si-Cr films have been vacuum-deposited from a tantalum boat,2 from a BeO-coated tantalum boat,3 by flash evaporation from an electron-beam-heated tungsten Source,4 and by triode sputtering.5 This paper describes a study of Si-Cr films vacuum-deposited by electron-beam heating of Si-Cr alloys. Resistivity, temperature coefficient of resistance, stability at 200°C, and structure were studied as a function of film composition. EXPERIMENTAL PROCEDURE Film Deposition. Si-Cr sources were prepared by vacuum-melting pressed pellets of mixtures of powdered chromium (99.9 pct, -100 mesh, Lunex Co., Pleasant Valley, Iowa) and silicon (99.99 pct, -325 mesh, United Mineral and Chemical Co., New York). A permanent-magnet focused electron-beam gun having a water-cooled copper crucible was used to heat the pellet until complete melting occurred. The mixture was then kept molten for an additional 5 min. The alloy thus formed was used as the source material for Si-Cr film depositions using the same electron-beam gun. Pieces of semiconductor-grade silicon ingots were used as sources for silicon depositions. The films were deposited within a standard vacuum evaporator having an 18-in.-diam Pyrex bell jar, a liquid-nitrogen-cooled trap, and a Consolidated Vacuum Corp. 6-in. diffusion pump containing Dow Corning DC-705 pump fluid. The substrates were thermally oxidized* silicon wafers 2 to 2.5 cm in diam. The

Jan 1, 1969

By Klaus Detert, Joseph Ziebs

The progress of primary recrystallization has been studied in alloys of nickel with 0.01, 0.1, and 1.0 at. pct Ta. It can be shown that in one particular alloy containing 0.1 Ta and 0.02 02 a large grain structure (0.5 mm diameter) could he developed by primary recrystallization in thin sheetswhich were cold-worked to 97.5 pct reduction in thickness. Electron transmission microscopy demmstrates that this phenonmena was linked to the occurrence of fine precipitates at subboundaries. A discussion of how fine precipitates can exert under certain circumstances a rather distinct retarding effect on nucleation rate is included. IN a former investigation, the recrystallization and texture formation in a series of binary nickel alloys including pure nickel were studied.' Nickel alloys with some tantalum added displayed peculiarities during primary recrystallization which have been studied in more detail by the present investigation. The alloys were prepared by powder-metallurgy techniques similar to the previous investigations.' Pure metal powders were thoroughly mixed to obtain alloys with 0.01, 0.1, and 1.0 at. pct Ta, referred to as alloy A, B, or C, respectively. The metallic impurities were kept below 0.005 at. pct except iron and cobalt with slightly higher values, by using highly purified nickel and tantalum powders.' The mixtures were pressed into bars and sintered at a temperature of 1300°C. The sintering atmosphere was either high vacuum, dry hydrogen, or wet hydrogen. The sintered rectangular bars were rolled 60 pct to a thickness of 3 mm, then annealed under dry hydrogen at 1000°C and again cold-rolled to about 97.5 pct reduction of thickness. After this heavy deformation, the sheet thickness was 0.07 5 mm. In order to study primary recrystallization which occurred in measurable times between 400" and 600°C, samples of the rolled sheets were annealed in a salt bath at various temperatures for various times in order to study the progress of recrystallization by hardness measurements and microscopic examination. For optical observation, the samples were polished and etched in a solution of 65 cu cm HNO3, and 18 cu cm acetic acid in 20 to 100 cu cm H2O, depending of the particular sample and annealing treatment. For transmission electron microscopic observations, thin foils were prepared by the combined window and Bollmann techniques.273 The electrolyte consisted of 23 pct perchloric acid and 77 pct acetic acid held at 15°C. Polishing was performed at a current density of 0.4 amp per sq cm. The examination of the thin films was accomplished by a Siemens Elmiscope-type electron microscope operating with an accelerating voltage of 100 kv. RESULTS The progress of primary recrystallization was very accurately followed in these alloys in order to establish the time when recrystallization started and ended during an isothermal anneal. Table I gives some of the data obtained by these studies. The time for beginning is a mean value, where somewhat less than 5 pct of the matrix has recrys-tallized. The end of recrystallization is the time when at least 95 pct of the matrix has recrystal-lized. Listed are three different B alloys, with 0.1 Ta distinguished by different sintering atmospheres which influence the rate of primary recrystallization. By the above method, the state of the grain structure when primary recrystallization was completed, but grain coarsening had not started, could be clearly defined. The average grain diameter of the recrystallized matrix is also given in Table I. The grain size did not depend on the temperature of the isothermal anneal. With one exception the grain size of the primary recrystallized matrix was found to be rather fine

Jan 1, 1965

By Howard E. McKinney

A high-pressure wellhead lubricator has been developed to facilitate telemetering electrical measurements from subsurface reservoirs to the surface with the well under normal flowing conditions. The field unit in use at the present time employs a 5/16-in diameter, single-conductor armored cable and is to be used in wells with surface pressures up to 5,000 psi. It has a pressure sealing element that maintains a continuous and absolute seal around the cable as it enters or leaves the tubing at speeds up to 175 ft per minute. A cable injecting device is used which obviates sinker bars or weight sections on the instrument. INTRODUCTION The development of instruments for securing physical measurements in pressure wells has been confined in the past to those instrument which would operate on a wire line and record the necessary measurements in the downhole instrument itself, or those which would operate on an electric cable in a well with the surface pressure killed by the use of weighted fluids or by the use of tubing plugs. In one case the accuracy of the measurements is questionable, and in the other the range of application is very limited. Considerable work has been done by other interests to provide effective means to accomplish the necessary telemetering. The U. S. Bureau of Mines developed a wellhead lubricator prior to 1947 which permitted a 5/16-in diameter single-conductor cable to be lowered into a well with a surface pressure of approximately 500 psi. This unit was used successfully in a number of tests in Oklahoma. A company which tests wells has recently offered on a service basis a wellhead lubricator with a 3/16-in diameter cable that reportedly operates up to 2,500 psi surface pressures. Each of the above operates on a staging principle to effect a seal. In both of these units some leakage of well fluid occurs when the cable is moved. SPECIFICATIONS FOR DESIGN In order to provide the maximum flexibility in its use, the following parameters were established for the design of our high-pressure wellhead lubricator: L An absolute well fluid seal up to 5,000 psi surface pressures. 2. Means for raising and lowering the instrument at speeds of at least 100 ft per minute. 3. Provision for the instrument to enter and leave the well without disturbing the well flow or the reservoir conditions. 4. A cable large enough to provide suitable electrical characteristics and suitable mechanical properties. 5. A method of operation that will not damage the well in any way. The present high-pressure wellhead lubricator field unit fulfills the above requirements. DESCRIPTION OF THE UNIT AND ITS OPERATION The cable selected for this use is the standard Amergraph 1H2 as manufactured by the American Steel and Wire Co. This particular cable is normally used by the Halliburton Oil Well Cementing Co. in their conventional well logging operations. Although the cable presents a noncircular cross-section (Fig. l), its diameter is very consistent; lor example, maximum diameter is 0.325 in., minimum diameter 0.314 in. This [actor permits the use of the sealing element, as later described. Early in the development of the high-pressure wellhead lubricator it was apparent that we could not effect a direct gas seal around a moving 1H2 cable. This becomes evident when an examination of the cable cross-section is made. The voids between the strands of the outer armor provide natural channels lor the flow and escape in large quantities of a low-viscosity fluid such as gas. However, it is relatively simple to

Jan 1, 1952

By R. I. Jaff, H. R. Ogden, D. J. Maykuth

A phase diagram for alloys containing from 0 to 66.9 pct Mn was determined. Two compounds, tentatively labeled 6 and y, were found in this range. The 6 compound is located at about 66.9 pct Mn and melts congruently at 1330°C. The ? compound has a composition near 53 pct Mn and originates in a peritectic reaction at 1200°C between liquid and 6. ß and Y enter into a eutectic reaction at 1175°C. The ß phase field terminates in a very sluggish eutectoid reaction between a and ? at 550°C. MANGANESE is one of the important alloying addition elements to titanium. As a ß-stabiliz-ing addition for a-ß and ß alloys, it provides high strength with adequate ductility.' Two of the earliest commercial alloys contain manganese as a major alloying component.' The earliest published data on the constitution of Ti-Mn alloys was that of Wallbaum,~ who reported the existence of the compound TiMn2. The transformation range of commercial-purity Ti-Mn alloys was investigated by Craighead, Simmons, and Eastwood' who found limited a solubility and a lowering of the ß transus to about 790°C at 7 pct Mn. Preliminary work by the authors of this paper, using high-purity titanium, confirmed the ß-stabilizing action of manganese and showed the existence of several intermediate phases in the Ti-Mn system." More recently, McQuillan3 determined the ß transus temperatures for high-purity Ti-base alloys containing up through 4.4 pct Mn. These data are given in Fig. 1. The present investigation covered alloys made with a high-purity base. The constitution of titanium-rich alloys made with commercial titanium has been reported4," by Holladay, Kura, and Jackson. The alloy range covered in the present investigation was from 0 to 69.5 pct Mn. This alloy range extends slightly beyond the composition of the first congruent-melting compound encountered on proceeding from the titanium end of the system. A description of the materials and methods used in the determination of the diagram is given in the Appendix. The partial phase diagram determined for the Ti-Mn system is shown in Fig. 2. Details on equilibria in the titanium-rich alloys are given in Fig. 3. Liquid-Solid Relationships Observations on the cast structures of the arc-melted ingots showed that the terminal solid solution of manganese in ß titanium enters into a eutectic reaction with an intermetallic compound labeled ?. As will be shown later, this compound has a composition around 53 pct Mn. The eutectic reaction temperature was determined as 1175°C by thermal analysis which also showed that the ? phase originates in a peritectic reaction at 1200°C. Fig. 4 shows typical eutectic structures for alloy compositions on both sides of the eutectic composition which is located at 42.5 pct Mn. In alloys over the range of 45.4 through 69.5 pct Mn, a second intermetallic compound, labeled 6, was identifield as the primary phase. This phase consistently increased in amount as the manganese content approached 66.9 pct, and, as shown in Fig. 5, an alloy structure containing 66.9 pct Mn consisted essentially of the 6 compound. Thermal-analysis data indicate a melting point of about 1330°C for the 6 intermediate phase. At 67.0 pct Mn, small quantities of a new, higher manganese-content phase were observed in the form of Chinese-script eutectic particles. Comparison of Fig. 6a and b shows an increasing quantity of this phase as the composition was increased to 69.5 pct Mn. The formation of peritectic ? in arc-melted alloys containing 45.4 pct Mn and above appears to be almost entirely suppressed, as shown in Fig. 7a and b. This is because of the narrow freezing range available for its formation by peritectic reaction and because of the very high cooling rates obtained in

Jan 1, 1954

By W. R. Hibbard

It has been proposed1 on the basis of slip and flow that the ideal deformation texture of drawn wire for face-centered cubic metals is a (111) direction parallel to the wire axis. Under these considerations, an intermediate [loo] texture is permissible but should eventually change to the stable [Ill] orientation. This theory does not explain why copper and its alloys containing up to about 30 pct nickel, 5 pct zinc and 1 pct aluminum were found to have a double [Ill], [100] texture, while alloys with at least 8 pct zinc and 2 pct aluminum developed essentially a single [Ill] texture.1,2 It does suggest, however, that the [loo] component of the former alloys should disappear with additional deformation.3 Some evidence exists to support this suggestion. Howald4 reported that annealed copper wire previously drawn 93.8 pct and 98.5 pct developed a single [Ill] texture. Since, in wire, the drawn and annealed textures are similar, these wires probably had a single [Ill] deformation texture before annealing. In addition, although cold rolled polycrystalline copper and 80-20 brass were found to form different types of pole figures,5,6 single crystals of these metals when rolled from the stable (110) [112] orientation were found to produce essentially the same polo figure.7.8 It may be, therefore, that while the addition of solute elements changes the path by which the final texture is obtained, the final texture is not changed. Experimental Results The wires remaining from the previous investigation1 already drawn about 50 pct reduction in diameter were further drawn to 86 pct and then to 96.4 pct total reduction in diameter. The textures were determined after these stages by transmission X ray photograms taken with a copper K-alpha beam rotated 0 degrees toward the wire axis. It was found that the ratio of the [111].] and [100] intensities of the double texture in copper and its alloys containing 0.94 pct aluminum, 30.70 pct nickel, 2.61 pct zinc and 4.99 pct zinc increased from about 3:l for the 50 pct reduction to about 9:l for the 86 pct reduction. After 96.4 pct reduction, these wires exhibited essentially a single [lll] texture. Summary Thus, the drawn wire deformation texture of copper and its alpha solid solution alloys containing aluminum, nickel or zinc is essentially a single [Ill] texture as predicted by theoretical considerations of slip and flow.' For copper and its alloys containing up to about 1 pct aluminum, 5 pct zinc and at least 30 pct nickel, an intermediate [loo] component is found after about 50 pct reduction in diameter, but disappears after about 95 pct reduction in diameter. For alpha solid solution alloys containing at least about 2 pct aluminum and 8 pct zinc the single [Ill] texture is developed considerably more easily and is found after about 50 pct reduction in diameter. No explanation of this compositional effect is apparent. Similar work is contemplated for cold rolled and cold compressed alloys. References 1. w. R. Hibbard, Jr. and M. K. Yen: Trans. AIME 175, 126. Metals Tech., Feb. 1948, TP 2334. 2. W. R. Hibbard, Jr. and D. E. Trout, 11: Trans. AIME 185, 620. Jnl. of Melals, Sept. 1949, TN 18. 3. W. R. Hibbard. Jr.: Disc. of R. M. Brick's paper on Deformation Textures, ASM Symp. on Cold Working of Metals, Oct. 1948. 4. T. S. Howald: Disc. of Ref. 1. Trans. AIME, 175, 126. Melals Tech. Aug. 1948, TP 2449. 5. R. M. Brick, D. L. Martin and R. P. Angier: Trans. ASM (1943) 31, 675. 6. 0. Dahl and F. Pawlek: Zlsch. Melall. (1936) 28, 266. 7. C. S. Barrett and F. W. Steadman: Trans. AIME (1942) 147, 57. 8. J. E. Burke and C. S. Barrett: Trans. AIME 175, 106. Melals Tech., Feb. 1948. TP 2327.

Jan 1, 1950

By F. W. Jessen, C. A. Johnson

The effect of treatment with ferrochrome lignosul-fonate on both sodium and calcium bentonites has been examined. In the early stages of treatment it appears that some base exchange of iron and chromium for sodium may occur with the sodium bentonite. Such exchange appears specific for exchange of sodium ions when the calcium ion concentration represents 40-5.5 per cent of the total exchangeable cations, and when additions of lignosulfonate are less than 1 lb per bbl. Adsorption appears entirely physical above 1 lb per bbl treatment level for all concentrations of calcium studied. Gel strength and plastic viscosity of both calcium and sodium bentonite systems were reduced with treatments of ferrochrome lignosulfonate up to 2 Ib per bbl, the greatest reduction occurring within a range of calcium concentration of 40-5.5 per cent of the total exchange capacity of the clay. INTRODUCTION The problem of control of viscosity and gel strength of drilling fluids by the action of thinners or dispersants has been studied by many investigators.1-7 In addition, much work has been done on formation of gel structure in clay suspensions. However, gel formation and structure still are incompletely understood, and the use of the various dispersing chemicals is based, to a large extent, on data almost entirely empirical in nature. In recent years the lignosulfonates have become increasingly important in the treatment and control of drilling fluids. More specifically, ferrochrome lignosulfonate has found rather wide acceptance, particularly in calcium systems.5-7 Lignosulfonates are refined lignin products made from spent sulfite liquor from which the fermentable sugars have been removed.15 The exact structure of lignin is not known; however, it is believed to be a phenolic propane type polymer which may exist as a branched chain or cross linked structure. The molecular weights of lignosulfonates probably range from 300 to 100,000 or more.15 A better understanding of the mechanism of adsorption of dispersants is essential before improvement and development of characteristics of drilling fluids and drilling fluid control is possible. This investigation was undertaken to determine the action of ferrochrome lignosulfonate on sodium and calcium montmOrillonite' LABORATORY INVESTIGATION A Stormer viscosimeter and Fann V-G meter were used to measure viscosity and gel strength. A Zeiss spectrophotometer was used for analysis of Fe and Cr and the flame attachment was employed in the analysis of Na, Ca and Mg. A General Electric X-ray diffraction unit utilizing Copper Ka radiation and a Ni-filter was utilized in the X-ray studies. PROCEDURE Two systems were studied. Predominately sodium clay, obtained from Wyoming, and a predominately calcium clay from Texas were used. These particular samples were chosen because of the extensive work of characterization completed by Mungan. Ionic base exchange capacity determined by flame photometry and total exchange capacity by the Kjehldahl method were obtained experimentally. A 7-per cent suspension of the sodium clay and a 20-per cent suspension of the calcium clay in distilled water were prepared by mixing with a high-speed mixer. The suspensions were allowed to stand for two weeks for complete hydration. Calcium chloride was added to portions of the sodium and calcium cla suspensions to obtain suspensions varying in Ca++ concentration as shown in Table I. A series of treatments was run with 500-ml portions of the original suspensions using a ferrochrome lignosulfonate. Treatment was carried out in the same way with each of the suspensions of varying Ca concentration. Viscosity and gel strength were measured and a filtrate obtained at each treatment level. Ten ml of filtrate were diluted to 50 ml, and aliquot portions of the 50 ml were taken for the Na, Ca, and Mg analysis by the flame photometer. The pH of these filtrates ranged from 7 to 7.3. Standard

By G. R. Speich

The precipitation of the Feab and Fe,Ti Laves phases (MgZn, type, C14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been studied in the temperature range 500" to 800°C using hardness measurements, light and electron microscopy, and X-ray and electron diffraction. The Fe-Nb alloys contained 0.96, 1.67, and 3.80 pct Nb and the Fe-Ti alloys 3.5, 5.8, and 8.8 pct Ti. In both systems only the equilibrium Laves phase is formed, with nucleation occurring at grain boundaries, at dislocations, and in the matrix. No cellular precipitation or transition phases were observed. The precipitation of the Laves phase in a fine dispersion leads to significant hardening in both systems. The hardness of the aged alloys is proportional to the reciprocal of the square root of the interparticle spacing. The maximum solid solubility of titanium in a! iron is 9.0 pct Ti at 1280°C. THE precipitation of the FezNb and FezTi Laves phases (MgZn2 type, C 14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been investigated as part of a continuing study of the mechanisms of precipitation from ferritic binary iron-base alloys. The iron-rich portions of the Fe-Nb and Fe-Ti phase diagrams are shown in Fig. l(a) and l(b). The Fe-Nb diagram is essentially that given by ansen' with the more recent work of Hume-Rothery and Gibson2 added. Goldschmidt3 indicates that the FezNb Laves phase has a solubility extending from 32 to 55 wt pct Nb. The Fe-Ti diagram is also essentially that reported by Hansen.l The recent results of Nishimura and kamei, Murakami, Kimura, and Nishimura,' indicate that the FezTi Laves phase has a solubility extending from 22.5 to 30.5 wt pct Ti. The L/6 + FezTi eutectic temperature of 1298°C indicated by Kornilov and oriskina' has been adopted. The addition of niobium or titanium to iron lowers the 6 — y transformation temperature and raises the y — a! transformation temperature. This results in a closed y field in the Fe-Ti system, but the lower solubility of niobium in a! (6) iron results in a eutec-toid, 6 — y + FezNb, at 1200°C, and a peritectoid, y + FezNb —-a, at 989°C in the Fe-Nb system. The maximum solubility of niobium is reported to be 4.5 wt pct in 6 iron,' 1.0 wt pct in y iron,7 and 1.8 wt pct in a iron.' Some results from the present work indicate that the maximum solubility in a! iron is actually less than 0.96 wt pct Nb. The maximum solubility of titanium in a! (6) iron is somewhat uncertain since the early work of To faute and Butting-haus indicated a value of 6.0 wt pct while later work of Kornilov and Boriskina6 yielded a value of 14.0 wt pct. The present work indicates that the maximum solubility is actually 9.0 wt pct. In both systems the phase in equilibrium with the iron-base solid solutions is a Laves phase (Mg znztype, C14), FezNb or FezTi. Both of these Laves phases have a wide range of Solubility. The precipitation-hardening behavior of Fe-Nb or Fe-Ti alloys has not been studied extensively. Genders and Harrison' reported that binary Fe-Nb alloys hardened upon aging. Peter and Fisher7 studied the mechanical properties of Fe-Nb and Fe-Ti alloys quenched from different phase fields.

Jan 1, 1962

By T. S. Lundy, R. A. Padgett

The fact that cobalt diffuses in silver at a much slower rate in a region near a free surface than in bulk material has been demonstrated in a variety of experiments. Various possible mechanisms of this near-surface effect (NSE) are examined in light of experimental evidences. The tendency for surface segregation of some solute atoms appears to be a likely mechanism to explain the effect. UNIDIRECTIONAL and isothermal diffusion from a plane source of radioactive tracer into an isotropic, homogeneous medium follows the Gaussian solution to Fick's second law, or: where A(x,t) is the position and time-dependent concentration of the diffusing species, M is the quantity of diffusant per unit area initially at x = 0, and D is the diffusion coefficient. For a given time, say t = tl, one can easily see that: d In Aixji)_____1_ r2] d(x2) 4Dti Thus, if diffusion data obtained by serial sectioning are plotted as In A(x,tl) vs x2, the diffusion coefficient is obtained from Eq. [2]. The ideal behavior seldom is observed in real systems. Deviations from ideality generally occur either at small or large values of penetration distance. The overall picture is shown schematically in Fig. 1 where Regions I, 11, and 111 are due, respectively, to some near-surface effect or effects (NSE), volume diffusion, and short-circuiting effects. For different systems and conditions of specimen preparation and analysis, the relative importance of Regions I, 11, and I11 may be drastically different. Region I is completely absent in many systems and there is no NSE. In others, however, there may be considerable difficulty in determination of volume diffusion coefficients due to the overshadowing influences of Region I. Such is particularly true when indirect techniques such as the surface concentration decrease or the Gruzin method' are used to find D. In this paper several experiments which had as their goal a better understanding of near-surface effects are reported. Specifically, it is well-known that unusual penetration behavior results for the diffusion of several impurities in ilver- and that considerable controversy exists with regard to interpretation of the published diffusion data. We chose to examine those unusual results which occur for cobalt diffusion in monocrystalline silver395 primarily because knowledge of experimental procedures and materials were readily available. Both radioactive co60 and co5' could be utilized to offer a wide range of available concentration of the diffusing species. Experiments were also performed on the diffusion of AgnO in silver. They gave base-line data for the system—both for technique evaluation and for examination of the vacancy distribution near the surface. I) PROCEDURES Cylindrical-shaped specimens 1.25 cm diam and 1 to 1.25 cm long were cut from 99.999 pct Ag single crystals obtained from Monocrystals Co., Cleveland. One end surface of each specimen was polished flat and etched with a mixture of 20 ml saturated Cr03 solu-tion-20 ml H20-3 ml concentrated HC1. Radioactive tracer (co60 or co5' or Ag'lO, each having a radio-chemical purity of greater than 99 pct) was deposited onto the prepared surface either dropwise with evaporation to dryness of the solution containing the tracer (0.5 N HC1 solution for the co60 and co5' and 0.6 N HNO3 solution for the A"'), by electroplating, or by evaporation from a tantalum or tungsten filament in an evacuated bell jar. The amount of deposited cobalt was varied from many atomic layers of cobalt containing the co60 to approximately one co5' atom per lo6 surface atoms of silver. This large variation in amount of deposited cobalt yielded information about both the influence of a thick-source layer of tracer and solubility effects on the NSE. Such variations were possible because of the large differences in half-lives,

Jan 1, 1969