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By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the 'a; and 'c,,' edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.' LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By John A. Hosking

The recent activity of numerous foreign mining companies in the once flourishing tin fields in Cornwall, England has resulted in renewed interest in the evaluation of hypothermal tin deposits. These deposits are mainly narrow tabular bodies and are usually steeply dipping. They exhibit thermal zoning the mineralization changing from lead/zinc through copper to tin with depth. The tin zone virtually never exceeds 1,000' in depth and the ore shoots within this zone tend to be erratic and localized. The grade which is presently considered to be economic is about 0.7% Sn. , this means a concentration of about l% cassiterite (the only economic mineral) which, being twice as heavy as the gange, represents only. 5% of the lode volumetrically. Within the lode, only one third may reach this economic grade and values within the shoots can range from 100% cassiterite to zero over a few inches. The enormity of the problem of evaluating such a deposit has not been fully appreciated by the companies involved whose experience has, for the main part, been in larger and more predictable ore bodies. This paper attempts to put these problems into perspective and out- lines the useful applicatations of statistical and computer techniques. It also stresses the need for enlightened interpretation of data by men familiar with the problem and that even in this day and age, educated, intuitive deduction should not yet be relegated to the limbo of alchemy and witchcraft.

Jan 1, 1969

By James Fisher

THE copper mines of the Keweenaw Peninsula in northern Michigan have long been of interest in connection with deep earth-temperature measurements. The extraordinary low geothermal gradient of 1° F. in 223.7 ft. announced by Agassiz1 as a result of measurements dating from 1886, although later" stated as in error, served to focus attention on this region as one offering, because of the great depth of the mines, unusual opportunity along this line. Lane,3 Van Orstrand4 and others have made valuable contributions to this study. Fresh opportunities afforded by the constant deepening of the mines, improvements in the accuracy and reliability of temperature-measuring instruments together with increasing knowledge of the heat conductivities and specific heats of the rocks, led the Michigan College of Mining and Technology in cooperation with some of the mining companies to renew work on this problem. It is planned eventually to complete a survey which will make use of the favorable opportunities for deep rock-tempera-ture measurements presented in these mines. This survey should include the determination of a depth-temperature gradient in both conglomerate and amygdaloid mines, and also the variations in temperature at the same depth in different geological formations. The first problem has a direct bearing on the question of providing equipment for necessary ventilation with increased depth. The second may show that a relation exists between the natural rock temperature and the mineral content of the formation.

Jan 1, 1932

By G. Barbery

Since the original paper, two methods have been introduced to compute the parameters of the three parameter size distribution equation: [ ] Both of them are based on graphical means, which are time-consuming and of little statistical significance. A program has been developed, using the Gauss-Newton method to compute by nonlinear regression analysis the parameters of the equation. Although the method is quite general in curve-fitting applications, it does not appear to be used in the field of size analysis, and a brief description is given. As applied here, the Gauss-Newton method involves the minimization of the least squares: [ ] where n is the number of sieves used. The second member of Eq. 2 can be approximated by a multiple Taylor's series expansion of first order about a starting value [ ] The minimization of Q (r,s,Xo) means: [ ] Putting Eq. 3 into Eq. 2 and differentiating, we obtain a system of equations which can be represented in matrix symbolism (box) The system can be solved for: [ ] and the operations repeated with new values: [ ] The starting values for r and s are taken as 1, for Xo, a value higher than the maximum sieve opening value. Applied to the data given by Herbst 5,6 for batch grinding of 7 X 9 mesh dolomite, the parameters given in Table 1 were obtained. The discussion of the significance of the residual sum of squares is a difficult subject in multiple nonlinear

Jan 1, 1972

By T. R. Cass, M. R. Achter

A technique for measuring the creep and rupture strength of nickel specimens bonded by sintered oxide layers has been developed for the investigation of the role of grain-boundary oxide in the oxidation strengthening of nickel during creep at 817 °C. Prom the inverse dependence of the rate of bonding on the thickness of the starting oxide, it is suggested that the rate of diffusion of Ni++ through NiO is the controlling process at the start of sintering. Cornparisons of the creep and rupture strength and of the microstructure of sintered couples with conventionul creep specimens suggest rupture in nickel is prevented by load-bearikzg, ikltergranular layers of oxide. A number of recent investigations have shown that at high temperature and low stress the creep-rupture strength of nickel and nickel-base alloys may be much greater in air than in an inert gas or vacuum.'-7 For example, at 817°C and 2500 psi, nickep failed in vacuum in 48 hr but not in air after 4000 hr, and a Ni-Cr-A1 alloy5 at 1038°C and 3000 psi failed in vacuum in 4 hr but not in air after 731 hr. Fig. 1 is a typical creep curve in air for materials experiencing this pronounced environmental strengthening. A common feature of these curves is the entry into a third stage of accelerating creep, concurrent with the for-

Jan 1, 1962

Human progress has a visible material phase, easily discernible, that is expressed in the standard of living. This material phase, however, is only the outward expression of a spiritual or mental phase that acts as a driving force in making humanity improve both its outlook and its mode of living. The instrument of progress is the human brain. Under the urge of spiritual drive, the brain acts as a focal point to utilize the forces of nature and put them to work for the benefit of mankind. Besides intelligence, which is an innate quality, the tools of the human brain are knowledge, experience, training, initiative, and skill. Given sufficient intelligence, the human brain can make an amazing amount of progress, provided it is supplied with an adequate spiritual and moral urge and a good technical background. It is the role of education to sup- ply such a background. The material phase of human progress proceeds on a series of parallel fronts, all of them interdependent to some extent (Fig. 7). The rise of the standard of living, dependent as it is upon the manufacture and mass distribution of goods, is based essentially upon the development and utilization of the material resources of a country or land area. This development involves the extraction of mineral and organic products from Mother Earth, their transportation to manufacturing centers, their transformation into finished goods and their dis-

Jan 1, 1950

By W. E. Hubbard

The Panhandle area of northwest Texas embraces the northern portion of the Permian Basin of Texas as well as a considerable portion of the western part of the Anadarko Basin of Oklahoma. For the purpose of this report it will include in addition to the 20 counties of the Panhandle proper the two tiers of counties lying to the south, a total area of about 32,000 square miles. Crossing the Texas Panhandle diagonally from northwest to southeast is the Amarillo Arch, related to which is all of the production discovered to date. Oil Production Up to Jan. 1, 1930, the Panhandle has produced about 125,000,000 bbl. of oil. The peak yearly production occurred in 1927, during which period 49,000,000 bbl. were produced. In 1928 the production fell to 25,000,000 bbl., but in 1929, on account of important discoveries in Gray County, the total increased to 31,000,000 bbl. To date Hutchinson County has produced 64 per cent. of the total. Table 1 shows the total yearly production by counties. The present production of the Panhandle is 100,500 bbl. from 1745 wells or an average of 57.6 bbl. per well compared to a production on Jan. 1, 1929, of 59,748 bbl. from 1468 wells or an average of 40.7 bbl. per well. The peak production of the year occurred during the week

Jan 1, 1930

"The largest variety of asphalt and related bitumen deposits in this country is found in Utah. Utah is one of the few places in the world where the hydrocarbon minerals, gilsonite or uintaite, wurtzilite (trade name elaterite) and ozokerite are produced. These bitumens occur in an area embracing nearly 10,000 square miles in eastern Utah near the Colorado line. This area is largely in the western part of the Uintah basin. The bitumens are in the Tertiary horizon in the various divisions of the Eocene series.Gilsonite is an asphaltite derived from petroleum, wurtzilite is an asphaltic pyrobitu¬men derived from petroleum, and ozokerite is a native mineral wax resulting from the met-amorphosis of paraffinaceous petroleum.Gilsonite is produced by the Gilson Asphaltum Company, a subsidiary of the Bar¬ber Asphalt Company, at Watson, Utah. A narrow guage railroad, seventy miles in length and with a 7 1/2 percent grade over the Book Cliffs on Baxter Pass, was constructed by the company from the Denver & Rio Grande Western railroad main line in order to open up the gilsonite deposits. The veins range from narrow upward to 18 feet in width. The Rainbow vein at the present wokings is eight feet wide, vertical, and has sandstone walls. This vein has been opened up for a distance of about three miles and in some places four hundred feet deep. Forty men usually are employed with a production of eighty tons per day."

Jan 1, 1925

The American Society of Mechanical Engineers extends an invitation to members of the Institute to participate in an exceedingly interesting excursion on Saturday, November 11. Permission has been secured for a visit to the plant of the Electric Boat Co. at New London, Conn. There will be run a special-test on a high-power 8-cylinder, 4-cycle Diesel engine. A large number of submarine and other engines in various stages of construction will be seen, also the boring of torpedo tubes, cylinders and other equipment for submarines. The drafting rooms and foundry mill also be open for inspection. The party will have an opportunity to see at close range the submerging of several submarines, and an attack on a vessel on the surface, an exhibit which is being arranged by courtesy of Rear Admiral A. W. Grant, who is in command of the submarine forces of the United States. The Boston members will leave South Station on train No. 7 at 8.30 A. M. Those from Providence will board this train at 9.36 A. M. The Worcester members will leave on train No. 745 at 8.36 A. M. The New York contingent will leave the Grand Central Terminal at 8.31 A. M. on train No. 8. This train will leave New Haven at 10.30 A. M. Upon arrival at New London, each group will go directly to the Mohican Hotel, where a "get-acquainted" luncheon will be served

Jan 10, 1916

By R. V. Whetsel, V. R. Garfias

Petroleum production in the Mexican fields during 1932, estimated at 32,400,000 bbl., was only 564,000 bbl., or about 2 per cent less than the 1931 total. Production in the northern fields declined approximately 1,100,000 bbl., the Tehuantepec output showed a drop of 340,000 bbl. and the South fields gained 865,000 barrels. Wildcatting continued at a reduced rate, the only successful completion being Presa No. 2 well which at a depth of 1535 ft. produced about 7,000,000 cu. ft. of gas. This well is an offset to Alberca No. 1 completed during 1931. General conditions in the petroleum industry coupled with the additional burden of the 21c per bbl. duty on oil imported into the United States further discouraged development activity in Mexico during 1932. Production of the Mexican fields in 1932 was distributed as follows: Production (U. S. Barrels) 1931 1932 _______________________________________________1________________________ Northern fields.................................... 14,092,000 13,000,000 South fields....................................... 10,535,000 11,400,000 Tehuantepec fields............................... .. 8,000,000 32,964,000 32,400,000 Since their discovery to the end of 1932, the fields have produced as follows: (U. S. Barrels) Northern fields..................................... 681,300,000 South fields........................................ 967,200,000 Tehuantepec fields.................................. 40,540,000 1,689,040,000 The tremendous productivity of the Mexican wells and the very small number actually drilled in the proven areas is shown in the following table:

Jan 1, 1933

By V. R. Garfias, R. V. Whetsel, J. W. Ristori

Preliminary estimates indicate that world consumption of petroleum and related fuels in 1938 will be close to 1,908,000,000 bbl., or approximately 7,000,000 bbl. less than in 1937. This total does not include military consumption in foreign countries, which for obvious reasons is not made public. Foreign military consumption in any one year, however, is approximately represented by the difference between the total production of petroleum and related fuels and the "partial total" consumption above noted, after adding any decrease, or subtracting any increase in stocks in the United States. Fig. 1 illustrates this "difference" and shows that in 1937 and 1938, owing to the wars in China and Spain and the possibility of armed conflict in Central Europe, foreign military consumption—and possibly additions to foreign stocks—increased nearly 70,000,000 bbl. in 1937 over 1936 and remained at this high rate throughout 1938. No official information on foreign oil stocks is available to the writers. Table 1, recently published, purports to give the oil in storage in some of the European countries, but it is not known whether the figures include oil stocks for military purposes. It should be noted that with the annexation by Germany of Austria and part of Czechoslovakia the consumption of the country has increased to 53,000,000 bbl., which is about 36,000,000 short of the German produc-

Jan 1, 1939

By J. W. Ristori, R. V. Whetsel, V. R. Garfias

Preliminary estimates indicate that world consumption of petroleum and related fuels in 1938 will be close to 1,908,000,000 bbl., or approximately 7,000,000 bbl. less than in 1937. This total does not include military consumption in foreign countries, which for obvious reasons is not made public. Foreign military consumption in any one year, however, is approximately represented by the difference between the total production of petroleum and related fuels and the "partial total" consumption above noted, after adding any decrease, or subtracting any increase in stocks in the United States. Fig. 1 illustrates this "difference" and shows that in 1937 and 1938, owing to the wars in China and Spain and the possibility of armed conflict in Central Europe, foreign military consumption—and possibly additions to foreign stocks—increased nearly 70,000,000 bbl. in 1937 over 1936 and remained at this high rate throughout 1938. No official information on foreign oil stocks is available to the writers. Table 1, recently published, purports to give the oil in storage in some of the European countries, but it is not known whether the figures include oil stocks for military purposes. It should be noted that with the annexation by Germany of Austria and part of Czechoslovakia the consumption of the country has increased to 53,000,000 bbl., which is about 36,000,000 short of the German produc-

Jan 1, 1939

By P. St. J. Perrott

AN explosive of balanced composition might be expected, on first consideration, to develop maximum propulsive strength.1 This hypoth¬esis is based on the assumption that an excess of oxygen would act simply as an inert material with a consequent lowering of flame temperature, also that a deficiency of oxygen would tend toward incomplete reaction of the combustible materials, thereby preventing development of the full strength of the explosion. Actually, however, it can be shown both theoretically and experimentally that an explosive having a certain oxygen deficiency will develop the greatest propulsive strength. This fact has been known to the technical staffs of explosives manufacturers for many years, but it has not always been recognized by explosives engineers in the field. For example: There is a fairly widespread opinion that the wrapper of a stick of dynamite is merely a container for the explosive and that it plays little if any part in the development of propulsive strength. Actually, it can be shown that the wrapper enters fairly completely into the explosive reaction. In the case of most gelatin dynamites, a given weight of explosive from which the wrappers have been removed will develop considerably less strength than the same weight of explosive plus wrapper, in spite of the fact that the latter combination contains less weight of the actual explosive ingredient. It can also be shown that a cartridge 7/8 in. in diameter may be stronger, weight for

Jan 1, 1928

By Gail F. Moulton

In spite of an increase of 7 cents per barrel in the posted price of oil for the Panhandle field effective June 16, 1943, there was less drilling during 1943 than ir, any of the several previous years. The drilling statistics are compiled as Table 2 and show the material increase in the percentage of the total number of field wells completed as dry holes. This increase suggests that the productive area of the field is largely drilled up on the well-spacing pattern now followed and that new discoveries will be required to permit any important new activity in the area. The fact that only four wildcats were drilled in the area during the year indicates that some new prospecting technique or some ncw point of view is required to stimulate exploration. No new producing areas were discovered during 1943 and no additions to oil reserves were made through extensions or discovery 'of new pays. Accordingly, the proven reserves in the area declined by the amount of the production, or nearly 31 million barrels. These results of drilling are similar to those obtained during 1942, whcn no new oil areas were discovered as a result of wild-catting, a total of five wildcat wells in 1942 resulting in four failures and one gas-fieid discovery of undetermined merit. sion. The number of oil-producing wells reported by the Commission increased during the year by 163 to a total of 5576 as of December.

Jan 1, 1944

By Gail F. Moulton

In spite of an increase of 7 cents per barrel in the posted price of oil for the Panhandle field effective June 16, 1943, there was less drilling during 1943 than ir, any of the several previous years. The drilling statistics are compiled as Table 2 and show the material increase in the percentage of the total number of field wells completed as dry holes. This increase suggests that the productive area of the field is largely drilled up on the well-spacing pattern now followed and that new discoveries will be required to permit any important new activity in the area. The fact that only four wildcats were drilled in the area during the year indicates that some new prospecting technique or some ncw point of view is required to stimulate exploration. No new producing areas were discovered during 1943 and no additions to oil reserves were made through extensions or discovery 'of new pays. Accordingly, the proven reserves in the area declined by the amount of the production, or nearly 31 million barrels. These results of drilling are similar to those obtained during 1942, whcn no new oil areas were discovered as a result of wild-catting, a total of five wildcat wells in 1942 resulting in four failures and one gas-fieid discovery of undetermined merit. sion. The number of oil-producing wells reported by the Commission increased during the year by 163 to a total of 5576 as of December.

Jan 1, 1944

By W. M. Wojcik, R. F. Kowal

Oxygen and sulfur distributions in commercial, 5-ton ingots of killed, medium carbon steel are described. Oxygen distribution is found to vary with deoxidation practice. Irregular distribution of oxygen within ingots makes necessary special precautions in sampling of rolled products for analysis of oxygen. Oxygen distribution is discussed in terms of recently published solidification concepts which had been successfully applied to simpler cases of segregation. These concepts have been found inadequate to explain observed oxygen distributions. Convective movements of the liquid metal, as determined by tracer elements, are shown to be capable of accounting for the observed distributions of oxygen. IN an effort to explore the origin of surface and subsurface imperfections in pierced steel products, a study of oxygen and sulfur segregation was made on ingots cast in open-top and hot-top molds. The results of our previous investigations1"3 have indicated the importance of the location and amount of oxide inclusions in an ingot. Inclusions close to the surface of the ingot have been found to contribute greatly to the formation of imperfections in the surface of finished products. This study of the effects of deoxidation and casting practice on segregation and the resulting oxygen distribution in ingots was initiated to determine the parameters controlling the location of inclusions in an ingot. Segregation of solute elements during solidification of low-melting binary alloys has been studied in the past.1, 5 Formation and growth of inclusions in iron melts have been studied under specific conditions."- In spite of these and other recent studies,10-12 segregation during solidification of commercial, killed steel ingots is not well understood. Consideration of solidification rates, of segregation during solidification of the chill, dendritic, and central zones, and of material balances for the segregated elements has indicated that a simplified theoretical solidification model is not adequate. However, the observed high oxygen contents in localized volumes of the dendritic zone can be rationalized if additional effects of convection currents in the ingots, precipitation, and rapid growth of new phases are considered. EXPERIMENTAL PROCEDURE Steelmaking and Processing. A group of nine killed. medium carbon steel heats having compositions listed in Table I have been studied. The deoxidation and mold practices used were varied to give a wide range of steel oxygen contents. The amounts of aluminum added to the ladle and the ingot casting practices (hot top and open top) were the main variables. The steel was made by a duplex practice in 160-ton tilting basic open-hearth furnaces. All nine heats were top-cast into 24 by 24 in. big end down, fluted molds, to a height between 60 and 76 in., using both open tops and exothermic hot tops. The deoxidation practice and the tapping and teeming details for each heat and ingot studied are given in Tables II and III, respectively. Hot-top practice is indicated by the letter H following the heat designation. Furnace and ladle temperatures were measured by standard disposable-tip, Pt/10 pet PtRh thermocouples. Teeming-stream temperatures were obtained as described by Samways et al.,13 by immersing a Pt/10 pet PtRh thermocouple, covered by a silica sheath, into the teeming stream under the nozzle. The output of this thermocouple was recorded with Leeds & Northrup Speedomax potentiometer. Calibration of the latter thermocouples was based on the freezing point of a pure iron/oxygen alloy (2795°F). The accumulated errors of measurements were within ±10°F. The thermocouple measurements were supplemented in this investigation by continuous recording of a ratioing, two-color pyrometer (Shawmeter), protected from smoke by a blast of clean air within the sighting tube, and calibrated to read with better than ±10°F accuracy. Following teeming of three heats, P, R, and T, tracer elements were added to the steel in the molds to obtain a record of the progress of solidification. As soon as the teeming stream was shut off, a 0.010-in.-thick steel can containing a mixture of crushed standard ferro-titanium and ferro-vanadium (0.05 pet of each alloy element) was plunged into the middle of the steel pool to a depth of 6 in. In about 30 sec no indication of the can or its contents remained. The surface of the open-top ingots solidified in 20 to 30 sec. A study of liquid metal movement and the precipitation of oxides was facilitated materially by use of the tracer technique as titanium has a low distribution coefficient between solid and liquid steel while vanadium has a high distribution coefficient.

Jan 1, 1965

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500' and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,' in the a Fe-Fe3C system are those of Bannyh, Modin, and odin' for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.'-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3'C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.' Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By S. T. Wlodek

The surface and subscale oxidation reactions were followed by means of continuous weight-gain and metallographic techniques over the range 1600" to 2200°F (871° to 1204 °C) for up to 400 hr. Full identification of all scale and subscale reaction products was obtained by electron and X-ray diffraction. At or below 1800°F (982°C) a linear rate of reaction (QL = 46.0 kcal per mole) governed the oxidation process, extending for up to 100 hr at 1600°F (871 "C). During linear oxidation the surface scale consisted of an amorphous SiO2 film overgrown with Cr 2O 3 and NiCr204. This initial linear process was followed, and above 1800°F completely replaced, by two successive parabolic rate laws (Qp = 60 and 57 kcal per mole). This parabolic reaction involved the formation of a complex scale consisting of Cr2 O3 and smaller amounts of NiCr2O4. Parabolic oxidation appeared to coincide with the disruplion of the silica film present during linear oxidation and was followed by subscale (internal) oxidation of crystobalite and NiCr2O4. The balance between the subscale and surface oxidation reactions controls the oxidation of this commercial alloy. The amorphous silica film appears to result in the linear rate and diffusion through Cr2O3 is the more likely rate-limiting step during parabolic oxidation. THE oxidation of a multicomponent composition is a complex phenomenon not presently amenable to a rigorous classical interpretation. Nevertheless, even a qualitative understanding of the scaling and subscale reactions that occur in a commercial composition can illuminate the reactions that limit its high-temperature stability in an oxidizing environment. This study of the oxidation of Hastelloy Alloy X presents the first of a series of studies with the above approach in mind. Hastelloy X exhibits one of the best combinations of strength and oxidation resistance available in a wrought, solution-strengthened, nickel-base alloy. Although during long time exposure some precipitation of M6C and M23C8 carbides as well as a complex Laves phase occurs, the amounts are probably small enough to have no appreciable effect on the chemistry of the matrix. Radavich has identified the oxidation products on Hastelloy X oxidized for 5 min to 10 hr at 1115°F as NiO and the NiCr2O4 spinel. Oxidation for 5 to 15 min at 1500°F produced a scale of spinel, NiO, and a rhombohedra1 phase, probably Cr2Os. Sannier et 2. have reported continuous weight-gain data for Hastelloy X at 1650" and 2010°F and internal-oxidation measurements after 150 hr at 2010°F. In addition, much of the data on binary Ni-Cr alloys recently reviewed by Kubaschewski and okins' and Ignatov and Shamgunova4 as well as studies of binary Ni-Mo alloys5 are also pertinent to the oxidation of this composition. EXPERIMENTAL Continuous weight-gain measurements and metallographic measurements of subscale reactions were the main experimental techniques used in this study. X-ray and electron diffraction backed up by a limited amount of electron-microprobe analysis served to characterize the nature of the scale- and subscale-reaction products. Two heats of commercial sheet of the composition given in Table I and identified as A and B were used in the bulk of this study. Internal-oxidation measurements were made on a third heat of material in the form of a 0.5-in.-diam bar. In order to assure homogeneity, all heats were reannealed 4 hr at 2175°F prior to sample preparation. weight-Gain Measurement. All specimens (1.5 by 0.4 by 0.03 in.) were abraded through 600 paper, electropolished, and lightly etched in an alcohol-10 pct HCl solution. An electrolyte of 150 cu cm H,O, 500 cu cm HsPO4 (85 pct conc), and 3 g CrO3 at a current density of 0.9 amp per sq cm or a solution of 10 pct HaW4 in alcohol used at 4 v and 0.3 amp per sq cm was used for electropolishing. The resultant surface exhibited a finish of 3 ± 1 p rms. Continuous weight-gain tests were made at 1600°, 1700°, 1800°, 1900°, 2000", and 2200°F on auer' type balances capable of recording a total weight change of 110 mg with an accuracy of k0.1 mg. All tests were made in air dried to a dew point of -70°F and metered into the 2-in.-diam reaction

Jan 1, 1964

By J. T. Norton, Joseph Gurland

IN spite of the extended use and high state of practical development of the cemented tungsten carbides, the structure of these alloys is still a matter of considerable controversy. The characteristic high rigidity and rupture strength of sintered compacts have been attributed to a continuous skeleton of tungsten carbide grains, formed during the sintering process. This view is based mainly on the work of Dawihl and Hinnuber,1 who reported that a sintered compact of 6 pct Co maintained its shape and some of its strength after the binder was leached out with boiling hydrochloric acid. After leaching, only 0.04 pct Co was reported to remain in the compact. They also showed that the assumed increasing discontinuity of such a skeleton, as the cobalt content is increased, could be made to account for the observed discontinuous increase of the coefficients of thermal expansion, the loss of rigidity, and the impaired cutting performance of alloys of more than 10 pct Co. Contradictory evidence was cited by Sanford and Trent,' who mentioned that a sintered compact was destroyed by reacting the binder with zinc and leaching out the resulting Zn-Co alloy. The skeleton theory also does not account for the observed change of strength of sintered compacts as a function of cobalt content. If the skeleton is responsible for the strength, the latter would be expected to decrease with increasing binder content. Actually, the strength increases and reaches a maximum around 20 pct Co. In addition, tungsten carbide is brittle and undoubtedly very notch sensitive. The highest value found in the literature for the transverse rupture strength of pure tungsten carbide prepared by sintering is 80,000 psi.3 herefore, such a skeleton does not easily account for a rupture-strength value of 300,000 psi and higher, commonly found in sint.ered tungsten carbide-cobalt compacts. In view of the conflicting data present in the literature, experiments were undertaken to determine whether the sintering of tungsten carbide-cobalt alloys leads to the formation of a carbide skeleton or whether the densification behavior and the properties of cemented compacts are consistent with a structure of isolated carbide grains in a matrix of binder metal. The specimens were prepared from powders of commercial grade. Tungsten carbide powder ranged in particle size from 0 to 5x10-4 cm. Mixtures of tungsten carbide and cobalt were ball milled in hexane for 48 hr in tungsten carbide lined mills. After milling, the specimens were pressed in a rectangular die (1x1/4x1/4 in.) at 16 tons per sq in. NO pressing lubricant was used. Sintering of the tungsten carbide-cobalt compacts was carried out in a vertical tube furnace equipped with a dilatometer (Fig. I), by means of which the change of length of the powder compacts could be followed from room temperature to 1500°C. An atmosphere of 20 pct H, 80 pct N was maintained inside the furnace. Decarburization of the samples was prevented by the presence of small rings of graphite inside the furnace tube. The temperature of the sample was measured by a platinum-platinum-rhodium thermocouple, which also was part of a temperature control system able to maintain a constant temperature within ±100C. Pure tungsten carbide compacts were prepared by sintering the carbide without binder or by evaporating the binder from sintered compacts in vacuum at 2000°C. Since complete densification of these samples was not desired, they were sintered only to 60 or 80 pct of the theoretical density of tungsten carbide. The specimens were prepared for metallographic examination by polishing with diamond powders and etching with a 10 pct solution of alkaline potassium ferricyanide. Cobalt etches light yellow and the carbide gray. The amount of porosity is exaggerated since it is difficult to avoid tearing out carbide particles, especially from incompletely sintered samples. Experimental Observations A number of specific experiments were carried out in order to study some particular aspect of the sintering problem. The details of these experiments, together with their results, are as follows: Electrolytic Leaching: The binder was removed by electrolytic leaching from sintered tungsten carbide-cobalt compacts for the purpose of determining the continuity of the carbide phase. The method used was based on the work of Cohen and coworkers4 on the electrolytic extraction of carbides from annealed steels. If the sample is made the anode, using a 10 pct hydrochloric acid solution as the electrolyte, the binder is dissolved, but the rate of solution of tungsten carbide is negligible. A current density of 0.2 amp per sq in. was applied. As shown in Fig.

Jan 1, 1953

By E. M. Porbansky

DURING the investigation of the electrical transport properties of copper, it became necessary to prepare large single crystals of the highest obtainable purity. In an effort to meet these demands, single crystals of copper have been grown by the conventional pulling technique—as has been used for the growth of germanium and silicon crystals.' Low-temperature resistance measurements made on these crystals show that, as far as their electrical properties are concerned, they are generally of significantly higher purity than the original high-purity material. The use of these pure single crystals with very high resistance ratios has made possible the acquisition of detailed information regarding the electron energy band structure of copper2-' and has stimulated widespread effort on Fermi surface studies of a number of other pure metals. It is the purpose of this note to describe our method of preparing very pure copper crystals by the Czochralski technique. Precautions were taken to prevent contamination of the melt from the crystal growing apparatus. A new fused silica growing chamber was used to prevent possible contamination from previous groqths of other materials such as germanium, silicon, and so forth. A new high-purity graphite crucible was used to contain the melt. This crucible was baked out in a hydrogen atmosphere at -1200°C for an hour, prior to its use in crystal growth. Commercial tank helium, containing uncontrolled traces of oxygen, was used as the protective atmosphere. A trace of oxygen in the atmosphere appears to be necessary for obtaining high-purity copper single crystals. A 3/8-in-diam polycrystalline copper rod of the same purity as the melt was used as a seed. The copper rod was allowed to come in contact with the melt while rotating at 57 rpm. When an equilibrium was observed between the melt and the seed (that is, the seed neither grew nor melted), the seed was pulled away from the melt at a rate of 0.5 mils per sec. As the seed was raised, the melt temperature was slowly increased, so that the grown material diminished in diameter with increasing length. When this portion of the grown crystal was -1 in. long and the diameter reduced to less than 1/8 in., the melt was slowly cooled and the crystal was allowed to increase to - 1-1/4 in. diam as it was grown. By reducing the diameter of the crystal in this manner, the number of crystals at the liquid-solid interface was decreased until only one crystal remained. Fig. 1 shows a typical pulled copper single crystal. The purity of the starting material and the crystals was determined by the resistance ratio method: where the ratio is taken as R273ok/R4.2ok. The starting material, obtained from American Smelting and Refining Co., was the purest copper available. Most of the pulled copper crystals had much higher resistance ratios than the starting material. The highest ratio obtained to data is 8000. Table I is an example of the data obtained from some of the copper crystals. Note that Crystal No. 126 had a lower resistance ratio than its starting material and this might be due to carbon in the melt. The melt of this crystal was heated 250" to 300°C above the melting point of copper. At this temperature it was observed that copper dissolved appreciable amounts of carbon. The possible presence of carbon at the interface between the liquid and the crystal will result in reducing conditions and negate the slight oxidizing condition required for high purity as discussed below. The possible explanations of the improvement in the copper purity compared to the starting material are: improvement in crystal perfection, segregation, and oxidation of impurities. Of these, the latter seems to be most probable. A study of the etch pits in the pulled crystals showed them to have between 107 and 108 pits per sq cm. The etch procedure used was developed by Love11 and Wernick.10 The resistivity of the purest copper crystal grown was 2 x 10-10 ohm-cm at 4.2oK; from the work of H. G. vanBuren,11 the resistivity due to the dislocations would be approximately 10-l3 ohm-cm, which indicates that. the dislocations in the copper crystals would contribute relatively little to the resistivity of the crystals at this purity level. Segregation does not seem likely as the reason for purification of the material, since the resistivity of the first-to-freeze and the last-to-freeze portions are approximately the same, as was observed on Crystal No. 124. On most of the crystals that were examined, the entire melt was grown into a single crystal. If the

Jan 1, 1964