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By L. H. Schwartz, S. K. Lahiri, M. E. Fine, D. Chandra

WHILE the yield stress of solution treated Fe-Cu alloys increases rapidly with aging, a precipitate has only been directly observed in overaged samples.'-" This precipitate is essentially pure fcc copper, the E phase. Hornbogen2 suggested that the initial hardening is due to clustering of copper atoms in a bcc iron matrix. Hornbogen was not able to obtain direct confirmation for such bcc clusters by either X-ray diffraction or electron microscopy; however, he did observe analogous clustering in Fe-Au alloys7 where the scattering factor difference between iron and gold is more favorable than that for iron and copper. Fujii, Nemoto, Suto, and Monma4 recently observed diffuse electron diffraction scattering in a 2.5 pct Cu alloy aged at 500°C: for 30 hr. They suggested that part of the diffuse SCattering was due to a modulated structure of 26 to 42 wavelength parallel to the (110) matrix plane. This disappeared with further aging. However, 30 hr at 500°C is well beyond the peak strengthening in this alloy which occurred at less than I hr at 500oc.4 By transmission electron microscopy they could not distinguish between quenched samples and samples aged to maximum strength. The purpose of the present investigation was to try to obtain further confirming evidence for a precipitation stage preceding the formation of the fcc E phase. Change in Young's modulus was selected for study be- EXPERIMENTAL PROCEDURE The Fe-1.67 at. pct Cu alloy was supplied by the U.S. Steel Corporation in the form of a hot forged rectangular bar. The carbon and nitrogen contents of this alloy were 70 ppm and less than 10 ppm, respectively. The samples for Young's modulus measurements were made by cold swaging to & in. diam and cutting to 2 in. lengths. Tensile test samples 1 in. long were prepared by cold rolling to a thickness of 0.012 in. and then machining to gage dimensions of 0.5 by 0.012 in. For Mijssbauer studies, foils 1 mil thick were prepared by cold rolling. During fabrication the alloy was given intermediate anneals at 845OC followed by quenching. The specimens after preparation were solution treated at 1000°C (y field) or 845°C (a field) for 1 to 2 and 5 to 6 hr, respectively, in a dynamic vacuum of about 2 x lom6 torr. The tensile and modulus specimens were drop-quenched into iced brine through an aluminum foil which vacuum-sealed the bottom of the furnace tube. The MOssbauer foils were drop-quenched into helium gas cooled by passing through N2 (liq) in a copper coil. The grain diameter of the modulus and tensile specimens was between 0.025 and 0.035 mm. The samples were aged from 400" to 500°C in a dynamic vacuum of 2 x 10-6 torr and cooled by pulling into a water-cooled portion of the vacuum system. The dynamic Young's modulus was measured at room temperature using electrostatic excitation and detection of longitudinal vibrations.' Neglecting any length change during the aging, (this is expected to be comparatively small), the fractional change of Young's modulus (?Et)/Eav, is equal to twice the fractional change of the resonant frequency (?ft)/fav . ?ft =ft —fo where fo and ft are the resonant frequencies of a specimen before aging and after aging to time t. The measured f's, approximately 51,000 cps, were corrected to 25°C for any variation in the ambient temperature. The tensile tests reported were carried out at room temperature in an Instron with a 1000 lb full scale load cell. The flow stress reported herein corresponds to a strain of 0.002. The Massbauer spectra were taken in a constant acceleration model AM-1 NSEC spectrometer. The

Jan 1, 1970

By A. E. Zawadzki

A progress report is presented on the development of a process for the removal of sulfur dioxide from flue gases. Catalytic oxidation of the sulfur dioxide in flue gases, with the production of recoverable sulfuric acid, has been demonstrated to be technically feasible. Problems associated with the process are discussed. The need for an inexpensive and efficient process for controlling sulfur dioxide emissions from utility plant stacks has been accentuated by the ever-increasing public demand for elimination of all man-made air pollutants. I would like to describe the results of an investigation of the development of such a process; more important, I would like to present a discussion of the problems associated with the process which remain to be solved. The research work on the BCR catalytic gas phase oxidation process has been jointly sponsored by the Association of Edison Illuminating Cos., Edison Electric Inst. and Bituminous Coal Research, Inc., since 1958. However, work on SO2-pollution abatement was initiated by BCR in 1953. Tieman and Clymer,1 working with ozone and simulated flue gases, evaluated a gas phase oxidation process for removing SO2 from flue gases. Their experimental data indicated that the use of ozone to oxidize SO2 in flue gas concentrations, with subsequent recovery of H2SO4, did not appear to be economical due to the large ratio of ozone to sulfuric acid produced (2.6 to 1). The cost of the ozone would be 6 to 10 times the cost of sulfuric acid produced. As a result of the ozone study, work on a catalytic oxidation process was developed. The following reactions are the basis for the catalytic oxidation process Reaction [I] normally occurs in the combustion of sulfur-bearing fuels. At the high temperature found in the combustion chamber, 95% to 99% of the sulfur in the fuel is oxidized to SO2 and 1% to 5% is oxidized to SO3. The concentration of SO2 in the combustion gases depends on the combustion efficiency and the quantity of excess air used. A commonly used rule of thumb is 0.1 percent by volume SO2 in the flue gas for each 1% sulfur in the fuel. Reaction [2] proceeds at a wide range of temperatures. The rate of the reaction is rapid above l,000°F; however, the equilibrium conversion drops rapidly above this temperature. 2 Reaction [3] occurs rapidly to completion at temperatures below 400°F; above this temperature some SO3 exists in equilibrium with H2SO4. Complete dissociation of H2SO4 occurs above 650°F.3 The simplicity of the proposed process provided added incentive to the development and evaluation of the various component unit operations. The advantages of the process were considered to be as follows: 1) no raw materials were required, 2) the unit operations were not radically new; and 3) a salable product, sulfuric acid, would be produced. The successful development of the process was contingent upon the solution of several major problems: 1) The development of a catalyst which would provide high catalytic activity at reasonable conditions of gas flow and temperature without causing an unacceptable increase in pressure drop. 2) The development of a high temperature dust collection system to provide clean flue gases to the catalytic reactor. 3) The complete recovery of the sulfuric acid produced in the process; the effluent gas must contain less than 20 ppm by volume of sulfuric acid. As of this date, the complete solution to these problems has not been achieved. EXPERIMENTAL Catalyst Development: The use of platinum and vanadium catalysts for the production of sulfuric acid by the treatment of dry gases containing 5% to 20% by volume sulfur dioxide has been known for many years. The application of the basic idea of catalytic oxidation of sulfur dioxide in flue gas concentrations was

Jan 1, 1965

By J. L. Brimhall, R. A. Huggins, M. J. Klein

IN a recent paper1 it was shown that small additions of magnesium, copper, and oxygen decrease the stacking fault probability in plastically deformed silver. Correlation of :X-ray data with measurements of the twinning frequency and metallographic observation of slip lines indicated that this effect may be due to an increase in the relative stacking fault energy. It is the purpose of the present note to report experiments on these alloys of known stacking fault probability that relate to the stacking fault contribution to electron scattering in silver. There has been a considerable amount of disagreement in the literature concerning the contribution of dislocations to electrical resistivity in metals. Calculations relating to the scattering of conduction electrons by the dislocation core, its strain fields, and related effects have been made by several authors.2-5 In addition, experimental work on Cu,3,6-10 Ni,11 and Ni-Co alloys1:! has shown that dislocations in those materials exert an anomalously large effect on resistivity, this effect being related to the presence of extended dislocations. The problem of the scattering due to the stacking fault region between partial dislocations has been treated theoretically using several different procedures.13-'0 The results of these calculations show a wide range of predicted values, from rather large to completely negligible, due to the models and the approximations involved. Almost all of this work has been applied to the specific problem of scattering in copper. The more complete theoretical treatments depend rather critically. on the shape of the Fermi surfaces and the effective mass parameters. The scattering from stacking faults might therefore be expected to vary significantly from one metal to another. Unfortunately, sufficiently accurate information is not available .which would allow one to have any confidence in a theoretical prediction of the scattering in the case of silver. Resistivity measurements were made on small wire specimens of vacuum melted high purity silver and several dilute alloys. These measurements were made at approximately 20°C, with great care being given to temperature measurement and corrections. At such temperatures phonon scattering is significantly greater than imperfection scattering. However, the experimental technique was such that measurements on similarly treated samples were reproducible to better than 2.4 X 10-9 ohm-cm, which was satisfactory for this work. Values of the stacking fault probability and the increase in resistivity after severe plastic deformation are given in Table I. The increases in resistivity resulting from plastic deformation agree quite well with previous work on silver.14,21-26 In addition, it has been previously found that interetitials and vacancies in silver anneal out well below room temperature, so that the residual imperfection scattering in these experiments could be expected to be primarily associated with dislocations;. It is seen from the data in Table I that large changes in stacking fault probability are accompanied by differences in resistivity due to imperfection scattering of only a few percent. If the scattering of conduction electrons by extended dislocations is primarily due to the area of the stacking fault region independent of the stacking fault energy, and not the core and strain fields associated with partial dislocations, the resistivity increase should be proportional to the product of the dislocation density and the stacking fault width, as is the stacking fault probability. Therefore, the imperfection scattering caused by plastic deformation of the alloys should be considerably smaller than that found in the pure silver. Since this was not observed, these results sugegest the possibility that stacking faults do not themselves contribute appreciably to the electrical resistivity of silver deformed at room temperature. An alternative explanation of these observations is that the scattering by the stacking fault is roughly proportional to the stacking fault energy, rather than being determined by the total area of such faults. Sufficient evidence is not yet available to separate these two possibilities. This work was supported by the Office of Naval Research.

Jan 1, 1962

By C. Kremer Bain

DURING the past several years of diamond drilling in Washington County, Mo., the St. Joseph Lead Co. has discovered a concentration of commercial lead-zinc ore at four different points within an area of 36 square miles. The largest and to date the most promising group of these orebodies is located in the Indian Creek area. It was considered to be of sufficient value to warrant development. The Indian Creek area is in the center of the northern half of Washington County, 11 miles northwest of Potosi, Mo., the county seat. The location is readily accessible from Potosi by car or truck over the all-weather Missouri State Highway No. 114. The topography is one of rolling relief, varying from an elevation of 700 ft above sea level on Mineral Fork and Indian Creek to a maximum of 1176 ft at High Point Tower. It is divided in equal halves between the drainage to Mineral Fork and to Indian Creek. The shaft site at 1060 elevation is on the divide between the two drainage areas. The Indian Creek side is rough and heavily wooded, with only a few cultivated clearings. The slopes to Mineral Fork are more gentle and rounded, with much of the area cleared for farm land. Most of the surface is covered with Potosi and Eminence formations, which show little evidence of any structure. Ore structure was worked out by extensive diamond core drilling, with holes varying in depth from about 700 to 1300 ft. As of Oct. 1, 1950, 218 prospect holes had been drilled within the 36-square mile area. The ore is disseminated galena with considerable accompanying sphalerite in the Bonne Terre forma-tion in the shape of irregular blanket-type deposits. The main controlling structural feature of the outlined mineral zone is a buried pre-Cambrian rhy-olite-porphyry ridge extending partly through the Bonne Terre formation, which laps against the por phyry and also covers it. The mineralized zone parallels and forms an irregular halo around the porphyry ridge and is concentrated in the Bonne Terre formation where the La Motte sandstone is cut out by the porphyry ridge. This is a very common mineral occurrence in the southeastern Missouri lead belt district. The La Motte sandstone, which normally underlies the Bonne Terre formation, is thus cut out entirely. In this area the Bonne Terre is usually about 275 to 320 ft thick, the La Motte varying in thickness from zero up to 400 ft. Commercial concentrations of ore are indicated at several places, the most notable being at the shaft site where an orebody at least 4000 ft long with widths of 500 to 600 ft has been outlined. The total thickness of mineralized rock reaches 150 ft in some holes, although total ore thickness runs from 8 ft to about 60 ft, often in more than one layer. Preliminary Planning Ore reserves as outlined lend themselves to open-stope mining with trackless haulage and mobile loading machines and drilling equipment. This type of equipment has proved to be very efficient during recent years in the company's lead belt operations. After a study of bids for shaft sinking and an estimation of comparative costs, it was decided that the shaft would be sunk by St. Joseph Lead Co. personnel using company equipment. Since the plant site is about 26 miles from the company's nearest lead belt operations, it was necessary to plan a complete surface plant, including mill, shops, office, change room, and warehousing facilities. Immediately following the filing of an application for a certificate of necessity, a headframe was selected for which detailed drawings were already available. The order was placed for fabrication so that it could be delivered and erected in time to serve for sinking the shaft. This eliminated the expense of a temporary headframe. Drilling was started on two churn drill holes near shaft location, and two 1000-gpm deep well pumps

Jan 1, 1954

By H. M. Otte, A. G. Crocker

SLIP, twinning, stacking faults, and precipitates on well-defined planes in a crystal produce traces that are visible on either a polished or an etched surface. The purpose of this note is to establish the usefulness and limitations of the information obtained from such traces when determining the orientation of single crystals or grains in a polycrystal. Attention will be confined specifically to traces produced by octahedral planes in cubic crystals, though most of the remarks can be taken as more generally valid. The problem of determining the crystal orientation is completely solved in principle' and in particular for the special case under consideration.1'2 Tables are available3 in which the orientations can simply be looked up when given the two or three angles between the traces. Thus a quick and simple method is available for obtaining the orientation of a crystal from surface traces. In this note two examples will be given from recently published papers and will show the use of the method with the aid of the Tables, as well as some of the precautions that should be taken in the procedure. As part of an analysis of X-ray Kossel lines, Peters and Ogilvie 4 determined from them the crystallographic orientation of the specimen. They chose a Cu-5.10 wt pct Si alloy that had been partly transformed from the a (fee) phase to the k (hcp) phase. The latter formed as very straight platelets along the octahedral planes of the a phase, and a photograph (Fig. 7 of Ref. 4) was reproduced in the paper4 of the region for which the orientation had been determined from the Kossel lines. Apart from a very small area (about 0.15 mm diam) near the top center of the photograph, the region shown was clearly all of one orientation. Traces in four different directions were readily identified. Starting with the smallest angle and proceeding counterclockwise, the angles between the traces were measured to be 27° 43', 55° 16', 64 3 43 1, and32"26'. These add up to 1802 08 1, indicating a cumulative error of 8'. The correct values should, of course, be taken from the original glass plates, or at least from prints on distortion-free paper, so the precision of the quoted values is actually greater than their accuracy. The solutions can be looked up in the Tables3 in four ways, depending on how the angles are paired, tion for the minutes of arc is required and the solution obtained will be identical for all the four pairs if the values of the angles are not in error. In a practical situation, such as this one, there are several sources of error, so that the four solutions obtained will all be slightly different. An arithmetic average of the four solutions is mathematically incorrect, but may, in special cases, give an answer close to the correct one. A rigorous procedure for refining the orientation has been described by Mackenzie;5 he gives a least-squares method that can be applied, if necessary, to this type of problem. The orientation thus determined can be compared with the one from the Kosel lines and discrepancies larger than the experimental error assigned to nonor thogonality of the X-ray or electron beam to the specimen. Here the example will only be used to illustrate the general procedure for making a very rapid rough check. From measurements on the stereographic projection, Fig. 9 of the paper,4 we can determine that the surface normal is approximately (0.434, 0.704, 0.562). From the Tables3 we find, using 28°, 55" as a good approximation to the first pair (27°43', 55°16'), that the surface normal is (0.453, 0.678, 0.579).* These two values are within 2 deg of each

Jan 1, 1967

By R. J. Grace

Primarily, this report presents the results of direct efficiency tests which were conducted on the 200-hp Coal-Pak, hot water generator, No. 3 unit, at the Otterbein College heating plant in Westerville, Ohio. Also included is a comparison of fuel consumption of the old plant with that of the new plant, a comparison of efficiencies obtained by the indirect method on a 300-hp Coal-Pak, and the cost of gas vs coal to show the savings effected by the latter. Tests were conducted with ten different bituminous coals selected by Mr. S. A. Frye, business manager at Otterbein College. The coals, of ten different suppliers, from four different states and eight different seams, represented competitive products economically available to the heating plant. The tests were conducted by the usual plant personnel which consisted of the plant superintendent and two assistants. No outside supervision of any kind was given during the tests. The tests were made from Dec. 13, 1960, through Mar. 4, 1961. During this period, 300.03 tons of coal were burned in the No. 3 unit. This tonnage represented 25.5 pct of the total coal requirements for the 1960-61 season. Operation during the period was typical for the comfort heat load which the plant supplies. Of the 78.12 operating days, the boiler was on bank or holdfire 14.31 days, or 18.32 pct of the time. The length of individual bank periods varied from 2 hr to three days. Run periods varied from about 2 hr to 7.26 days. DESCRIPTION OF PLANT AND HEATING EQUIPMENT The new Otterbein College heating plant, completed in the summer of 1957, is located in a 50x50 ft boiler room on the lower level of a combination maintenance building and heating plant. The building is situated away from the main college complex on a hillside, which allows for on-grade delivery of coal to the three bunkers. The bunkers are located directly above and connected with the individual stoker hoppers. Fig. 1 shows an in-plant view of the Coal-Pak installations. The No. 3, hot water, unit is at the extreme right. The heating plant consists of three 200-hp Coal-Paks. Unit No. 1 is operated at 4 psi and carries the steam heating load of 14,000 sq ft EDR (steam) installed in two buildings. Provision has been made to convert these buildings to hot water heating at some future date. Since the unit under maximum load conditions operates only at about 50 pct steaming capacity, a heat exchanger was installed to convert steam to hot water. Thus, during light loads in mild weather the unit can be employed more efficiently to supply both steam and hot water and eliminate the need for operating either of the two hot water units. Units No. 2 and No. 3 serve a hot water heating circuit for a large group of 21 buildings of the College. These boilers deliver hot water at temperatures up to 200°F to the various buildings through distribution lines in tunnels. The present calculated maximum heat loss for the College is 15.195 million Btu per hr. The Coal-Paks have individual design capacities of 6.700 million Btu per hr. Table I lists the design date for the Coal-Paks. The No. 3 unit was chosen as the test unit, primarily because of its bunker location at the far end of the delivery ramp. Because of this location any excess coal above bunker capacity could be conveniently stored and isolated from the adjoining bunkers. Each bunker has a capacity of 30 to 35 tons of coal. The No. 2 and No. 3 hot water generators are equipped with automatic controls which maintain the

Jan 1, 1962

By M. J. Pool, P. J. Spencer, R. V. Miner

The partial molar heat of solution of rhodiunz in liquid lin and Rh-Sn alloys has been measured as a function of rhodium concentration at 700" , 725" , 750" , and 775°K. The values at infinite dilution are very exo thermic, ranging from -29,950 to -28,260 cal per g-atom Rh at 700" and 775"K, respectively. At the solubility limit the heat of solution becomes sharply nzore exothermic and has permitted the liquidus boundary to be accurately established at each temperature. From the measurements in the two-phase region of liquid Plus RhSn, the heat of formation of RhSn,has been determined. A large increase in the heat of formation between 725" and 750°K suggests the possibility of a phase transformation in this compound. V ERY few measurements have been made of the heats of solution of transition metals in liquid tin; yet those values that are available are of great interest because of their very large exothermic nature. For example, the heat of solution at infinite dilution of palladium in tin has been measured as about -26,000 cal per g-atom (625" to 800°~),' while the heat of solution at infinite dilution of platinum is even more exothermic at -28,591 cal per g-atom (914°K).' These values are of the same order of magnitude as the heat of formation of many intermetallic compounds and as such clearly indicate that very strong bonding must exist between the solute and tin atoms in the liquid solutions. Rhodium might be expected to display similar solution characteristics in tin in view of its close electronic resemblance to palladium and platinum. Since no thermodynamic data are available for Rh-Sn alloys, rhodium was chosen as an appropriate solute for further investigation of transition-metal systems with highly exothermic heats of solution at infinite dilution. EXPERIMENTAL The heat of solution of rhodium in dilute Rh-Sn liquid solutions was measured as a functlon of rhodium concentration at 700°, 725", 750°, and 775°K. The liquid-metal solution calorimeter used in this work has been fully described elsewhere. At the start of each series of measurements, the solvent bath consisted of about 0.5 g-atoms of 99.9+ pct pure tin. To this was made a number of small rhodium additions, about 0.0005 g-atoms each, and the heat of solution was measured for each. Rhodium of 99.9+ pct purity in powder form was used in order to promote rapid dissolution in the liquid tin. The powder specimens were contained in tin foil stated to be purified (lead-free). This foil was found to have no measurable heat of solution in pure tin so the effect of any impurities could be neglected. The energy equivalent of the calorimeter was experi- mentally determined by dropping tungsten and/or tin specimens at intervals during each series of rhodium drops. The tungsten and tin used were 99.95 and 99.999+ pct pure, respectively. The only heat effect due to a tungsten drop, or a tin drop at low rhodium concentrations in the bath, is the sensible heat of the specimen. The heat content of these materials is well-established and is presented in the compilation of Hultgren et al. 4 As the rhodium concentration in the tin bath increases a small heat effect arises from the reaction: Sn (liquid, T) — & (soln, T) where T is the temperature of the tin bath. Where necessary, this heat of solution of tin was determined by Gibbs-Duhem integration, and corrections were made to the heat effect of the tin calibration specimens and the tin foil containing the rhodium specimens. RESULTS AND DISCUSSION The calculated values of the heat of solution of rhodium in dilute Rh-Sn alloys as a function of composition are shown graphically in Fig. 1. The values have been corrected for the sensible heat of the specimens, initially at 273"K, and apply to the reaction:

Jan 1, 1969

By R. J. Lloyd

INTRODUCTION The Mount Isa Mine is a large modern underground mine located in North-Western Queensland, Australia. Two ore types are mined and treated separately. Currently silver-lead-zinc ore is mined at the rate of 2.6 million tonnes per annum and copper ore at the rate of 4.6 million tonnes per annum. The silver-lead-zinc orebodies are mined by sub level open stoping and cut and fill methods whilst all copper ore is extracted by various forms of sub level open stoping. The mining operations are highly mechanised and utilise diesel powered load-haul-dump units of various sizes, two and three boom face drilling jumbos, electric-hydraulic rotary-percussive ring drills, in-the-hole hammer drills, rotary blasthole drills, raiseborers, battery/trolley locomotives, a large fleet of rubber tyred service and supply vehicles plus light rockdrills mounted on airlegs, rail mounted overshot shovels and battery and diesel powered locomotives. All stoping production ore is extracted with diesel powered load-haul-dump units. The ore is tipped into orepasses which connect to the main rail haulage levels. On the haulage levels electric battery/trolley locomotives are used to pull rakes of bottom dump or side dump trucks which feed the ore into primary crushers. Following two stage crushing the ore is conveyed to the shaft and hoistod to surface in bottom dump skips. Each ore stream has its own rail transport system, crushing stations and hoisting shaft feeding separate concentrators. This paper will consider some aspects of the role of equipment and machinery in the growth of the mine, will discuss in some detail the machinery and equipment in use today and will conclude with a look at some possible developments in mining equipment for the future, with particular reference to the Mount Isa Mine. A summary of mining equipment in use at Mount Isa is given in the Appendix. THE PAST Silver-lead-zinc ore was discovered at Mount Isa in 1923 and within a very short time many small mines were being developed. However the rich surface ore traces did not continue and by 1928 Mount Isa Mines Limited had acquired sufficient leases to plan for a large scale mine to exploit the low grade orebodies. At this early stage it was recognised that the mine would need to adopt the most mechanised mining techniques then available in order to overcome its twin disadvantages of low graaes and extreme remoteness. The Company introduced bar mounted drifters and overshot shovels to replace hammer and tap and hand shovelling in development work and by 1930 headings were advancing at the rate of 30 metres per week. In keeping with the concept of mechanisation the early engineers designed the Man and Supply shaft with a very large, for those days, cage compartment measuring 3.8 m x 3.4 m. This shaft was the main means of access into the mine for 36 years until the K57 shaft (now R62 shaft) was commissioned in 1966. Man and Supply is still in regular use. Production commenced in 1931 at an annual rate of approximately 660 000 tonnes of silver-lead-zinc ore. The mine was mechanised to an extent which was previously unknown in Australia; whilst the concentrator, smelter and power house utilised the most modern and efficient equipment available. Even so, the mine was very near to closure on several occasions and did not return a dividend to its shareholders for many years. Production levels remained at or slightly below 660 000 tonnes until a separate copper ore streani and mill was commissioned in 1953, doubling the existing production levels. The first underground crushers were installed at this time. Production rates expanded in the years between 1953 and 1973. By 1960 production reached 2740 000 tonnes of ore. In 1965-66 total production was 3650 000 tonnes and in 1973 the production rate plateaued at the current level.

Jan 1, 1981

By G. R. Love, M. L. Picklesirner

THE use of color adds a new beauty, power, and versatility to metallography. This has been amply demonstrated in a number of public exhibits and on the walls of corporate, government, and university metallographic laboratories around the world. Indeed, in a number of cases, the color not only is of esthetic value but is scientifically essential to the competent examination of particular samples and systems. Optical strain analysis,' determination of true grain size in U-A1 alloys: phase identification in Nb-base alloys,3 analysis of transformation rates in heat-treated Nb-Zr alloys,4 measurement of solidification segregation in cast Nb-Zr alloys,' study of the intermediate phases in Nb/Sn diffusion couples,6 investigation of the oxidation kinetics at various surface orientations in single crystals,7'8 and a number of other research efforts9'10 would have been vastly more difficult without the extra clarity and distinction introduced by color—either the colors resulting from particular polarized light techniques or the interference colors obtained by oxidation. It is unfortunate that the beauty of colored micro-structures cannot be shared more widely, but the economics of publishing a technical magazine apparently prohibits color plates except under extraordinary circumstances. It is doubly unfortunate that no convenient, general method exists for communicating the information available in colored microstructures to the scientific community. True, in some instances the color changes observed are dramatic enough that direct black and white photography is adequate. In photoelastic stress analysis, several orders of interference fringes may be produced and it is frequently desirable to suppress the color effects (use monochromatic light) to simplify interpretation. On the other hand, relatively minute color variations may be readily detectable by eye, be of considerable assistance in interpreting a structure, and yet be enormously difficult to reduce to an unambiguous black and white print. In order to illustrate a possible compromise or solution to the above problems, we wish to show three black and white photographs of the same region of an Nb/Sn diffusion couple whose interpretation depends heavily upon use of color techniques. These micro-structures were obtained from a section through a rod consisting of commercial-purity niobium tubing filled with 99.995 pct Sn (melt-filled in 10"6 Torr vacuum). The composite rod, measuring 500 mm long, was bent into a hairpin shape and inserted into water-cooled copper grips in a vacuum high-temperature furnace. The rod was outgassed for 2 hr at a furnace temperature of 800°C and was further heated by self-resistance using a 2.2-kva ac power supply. The rod was raised to 1910°C over a 4+-hr period, held for 15 min, slow-cooled to 1500°C over a -hr period, and free-cooled to room temperature (all temperatures were measured with W5Re/W26Re thermocouple). Throughout the heat treatment the ambient pressure was kept below 8 x lo-' Torr. Metallographic preparation of the sample was completely conventional except that it was necessary to extend the grinding steps to remove damage in the brittle NbsSn phase introduced by sectioning. No satisfactory chemical or electrochemical etch has been found for these diffusion couples; of those which have been tried, any that attack the niobium-rich phases at all attack the tin-rich phases disastrously. However, the final polishing steps did produce a slight relief effect and this, coupled with anodizing, yielded excellent clarity in the microstructures for direct observation. The anodizing voltage was chosen to give maximum change in color per unit change in composition. In this case, indeed normally, this maximum sensitivity occurred in the blue-to-red color range. The pure niobium tube wall anodized to a relatively bright blue

Jan 1, 1967

By E. A. Hopkin

Laboratory tests conducted by the author. together with actual field experience in Canada. have indicated the magnitudc of some of the factors affecting ability of drilling mud to clean the hole. A correlation was observed between funnel viscosity and particle slip velocity. A relationship was also observed between the Bingham yield value of the mud and the particle .slip velocity. Laburatury tests indicated little change in slip velocity with funnel viscosities up to ahout 80 sec/qt or to yield values of aboul 15 lb/100 .sq ft. The lip velocity of the partic1e.s. studied vuried from 160 ft/min with water to neerly zero for high mud viscositie. lncreasing the mud density, creating laminar annular mud flow or rotating the drill pipe Mlay also improve the carrying capacity of mud. Field tests indicated that during fast upper-hole drilling, the rate of cutting removal must he sufficien to maintain the concentration of cuttings in the annulus at less than 5 percent by volume to prevernt balled-up drill collars and .stuck drill pipe. INTRODUCTION In the Mid-Continent area, hole cleaning during rotary drilling normally involves the use of low-density drilling muds with funnel viscosities varying from 26 to 80 sec/qt. However, frequently it is necessary to raise the mud viscosity in excess of 200 sec/qt to clean the hole. In addition, field experience has indicated that during very fast upper-hole drilling, annular mud velocities considerably in excess of the maximum slip velocity of the cuttings (normally considered to be 120 to 150 ft/min) are necessary to prevent balling the bit and drill collars. In view of these variations in mud properties and circulation rates necessary to clean the wellbore, a study of factors affecting hole cleaning and the relative magnitude of each was undertaken. The study was also prompted by the knowledge that a drilling mud with properties close to those of water would drill at rates several times that of a viscous mud. The carrying capacity of these near-water muds was not clearly understood, however, and many drillers were reluctant to use them. DISCUSSION EFFECT OF MUD PROPERTIES ON DRILLING RATE The effect of mud properties on drilling rate has been studied by a number of investigators. 1t is clear from their work that mud properties close to those of water will significantly improve drilling rate and bit life. If the water-type mud will also effectively clean the hole and cause no logging or formation impairment problems, the choice of an appropriate drilling fluid is clear—use water. Often, however, a water-type drilling fluid is not capable of effectively cleaning the hole. THEORY OF PARTICLE SETTLING The forces acting on a particle that is allowed to settle through a fluid quickly reach equilibrium, and the particle settles at some constant velocity referred to as the slip velocity. The slip velocity of any particle depends upon a number of factors such as density and viscosity of the fluid, the volume, specific gravity, shape and roughness of the particle, and upon the shape and area of the projected face of the particle at right angles to the direction of relative fluid solid movement. Brown' expressed this relationship for spheres in Newtonian fluids in the following equation. where v, = slip velocity D, — diameter of sphere p, = density of spheye p, = density of liquid /a = friction factor g = constant. The friction factor f, varies as the size, shape, surface roughness and slip velocity of the body, and as the density and viscosity of the fluid varies. WaddelV ound experimentally that where dynamic similarity exists. f, was a function of the particle Reynolds number (NRe) of the sphere (Fig. 1). Fig. 1 shows that f, for spheres varies from over 10 for low NKe numbers to 0.44 for N,,. over 600.

By E. A. Gulbransen, K. F. Andrew

Thermodynamic information on the solubility of hydrogen in exothermic metals is limited. Thus, the overall solubility decreased as the temperature rose, which suggests the heat of solution of hydrogen in the metal is negative; yet the terminal solubility in the metal phase increased, which suggests an endothermic reaction. A thermodynamic analysis, therefore, was made of the several equilibria involved when hydrogen dissolved in the metal. Equations were derived expressing the solubility, terminal solubility, and decomposition pressures of hydrogen in terms of the heat, entropy, and free energy of solution of hydrogen in the given phase. The relations between the thermodynamic functions for the a-zirconium and 8-hydride phase were developed. The thermodynamic quantities were determined experimentally by the measurement of the decomposition pressures over a broad composition and temperature range. Two new methods of analyzing the experimental data were developed for determination of the terminal solubility. STUDIES', ' of the impact strength of zirconium at room temperature indicated that small quantities of hydrogen, of the order of 10 parts per million, embrittles the metal. Micrographic' and X-ray diffraction' studies showed this embrittlement to result from the precipitation of a second phase upon slow cooling. These studies suggested that the terminal solubility of hydrogen in the metal phase increased with increase of temperature. This behavior appeared to contradict the effect of temperature on exothermic hydrogen occluders such as zirconium. For these metals, the solubility of hydrogen should decrease with increase of temperature. Before these facts could be understood, a thorough analysis of the several equilibria was essential. It was the purpose of this paper to consider the several equilibria involved when hydrogen was reacted with zirconium from both the theoretical and experimental points of view. Since the overall solubility of hydrogen in the metal has been considered by a number of workers, it was proposed to study the composition range 0 to 6 atomic pct H in detail. Literature Schwartz and Mallett' determined the terminal solubilities of hydrogen in the metallic phase from diffusion studies. They extrapolated concentration-penetration curves to the boundary between the solid solution phase and the hydride phase at the surface. Their results showed values of 2.6 atomic pct at 400°C and 5.2 atomic pct at 500°C. Extrapolations of the data to room temperature suggested very low values for the terminal solubilities. This study confirmed the hydrogen embrittlement results and indicated that the terminal solubilities increased as the temperature was raised. The solution of hydrogen in zirconium over the complete concentration range was studied by Hall, Martin, and Rees3 and by others. The results showed that hydrogen was absorbed up to a maximum composition of 66 atomic pct or ZrH This composition represented the t-hydride phase. The maximum amount of hydrogen absorbed increased with pressure and decreased with temperature. Due to this temperature behavior, zirconium was classed as an exothermic occluder." In 1930 Hägg studied the crystal structures of the Zr-H alloys over a broad composition range. Four hydride phases were found. However, the range of homogeneity of the several phases was not studied. Gulbransen and Andrew" recently studied the phase diagram of this system by X-ray diffraction methods and by a thermodynamic method based on decomposition pressure measurements. The results showed that only two hydride phases existed for low temperatures, the 6 and the .-phases of Hagg.' Both phases had broad regions of homogeneity. The lower limit of the two-phase region of a and d-phases suggested a terminal solubility of 4 atomic pct at 500°C. This value was in agreement with the results of Schwartz and Mallett.' To avoid hydrogen embrittlement at low temperatures, it was necessary to heat the metal in high vacuum at elevated temperatures. To choose the conditions of temperature and high vacuum, it was

Jan 1, 1956

By R. W. Armstrong, D. H. Feisel

Self-diffusion in pure crystalline solids has been described through extension of the Cohen and Tum-hull volume -fluctuation model originally proposed for diffusion in simple liquids. It is shown, for a number of crystalline solids, that the self-diffusion coefficient, D, obeys the relationship where a is the lattice spacing, v the Debye frequency, Z' the lattice-volume fluctuation per atom required for a diffusion jump, and (?V/Vo) the relative increase in the lattice volume resulting from thermal expansion between O°K and the temperature under consideration. The calculated value of Z' is dependent upon the difiusion mechanism and the lattice geometry. ThE need for an increased understanding of mass-transport processes in crystalline solids has resulted in much research to determine rates of self-diffusion.' For several metals (e.g., copper, silver, and iron), the experimental values of the self-diffusion coefficient, D, have been determined over a large interval of temperature and the accuracy of D has been investigated through repeated experiments. Also, a number of empirical and theoretical diffusion studies have established a rational basis for understanding the D values for the different elements.2"6 The empirical diffusion analysis by Sherby and simnad6 supplied the main stimulus for the present study. Sherby and Simnad, reviewing the self-diffusion data for a substantial number of pure crystalline solids, suggested that sufficient data were available to establish with some certainty the apparent intrinsic material properties which influence D. Without explicit regard for any mechanism of diffusion, these investigators obtained an empirical relationship for D which correlated the self- diffusion coefficient for each element with the melting temperature, crystal structure, and valence of the particular element. Their analysis is only unsatisfactory in that the effect on D of crystal structure is not very clear and the valence to be assigned to an element is not always straightforward. The present study is an attempt, from a very different viewpoint from that of Sherby and Simnad, to establish a basis for understanding the self-diffusion coefficients for crystalline solids. This analysis was undertaken for the purpose of developing a general expression for D which would explicitly depend on the mechanism of diffusion. The main result of the study is that diffusion in crystalline solids may be described in terms of a volume-fluctuation model which was originally proposed by Cohen and Turnbull7 to describe diffusion in simple liquids. The model appears to be useful for predicting self-diffusion coefficients in crystals. The following sections describe the volume-fluctuation model for diffusion, the application of this model to crystals, and the resultant agreement with experimental data. 1) THE VOLUME-FLUCTUATION MODEL FOR DIFFUSION Cohen and Turnbull7'8 developed their model for liquid self-diffusivity for the purpose of describing certain properties of liquids, glasses, and the liquid-glass transition. A hard-sphere model for the liquid structure is used. In this model, the size of a spherical molecule or atom is fixed for all temperatures by the interatomic spacing at the absolute zero of temperature. At any temperature above O°K, the atom is viewed as being contained within a larger spherical cage defined by the interatomic spacing of the atoms at that temperature. A random distribution of varying cage sizes is assumed to exist in the liquid. An individual diffusion jump occurs when the free volume of an atom (the volume of the cage containing the atom minus the volume of the atom) is large enough for the atom to jump out of its cage. With this physical picture of diffusion in liquids, Cohen and Turnbull derive the following equation for self-diffusivity: D=Doe-yv*/vf [1] where Do is the product of three factors which are the diffusion-path geometry, the diffusion-jump distance, and the velocity of the diffusing atom, v*

Jan 1, 1964

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper .to, discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in. brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: 1-gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2-liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3-glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4-crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that carried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant, contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.1 At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1-aqueous solution, a much more expansible liquid, and a gas; 2-aqueous solution, salt crystals, and a gas; and 3-the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20° and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.2-6 Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid. carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.7,8 Hartley (1876, 1877),9,10 Hawes (1881),11 Wright (1881),12 Johnsen (1920),13 and Holden (1925)14

Jan 1, 1952

By AIME AIME

FOR the use of workmen and employees, the company should establish a dispensary and a -hospital where workmen who suffer accidents or professional diseases may be taken care of; and at suitable places in the mine or metallurgical plant it should install first-aid stations. Workmen have a right to receive 75 per cent of their wages while they are unable to perform their work as result of a professional disease; but some companies pay full wages and in the case of natural disease, with the exception of venereal, alcoholism, injuries from fights, and chronic illnesses, 50 per cent of their wages up to a period of two months. The number of diseases the Law considers as professional is large and increases almost daily. Among the professional diseases, the one which has caused greatest harm to the miners and expense to the companies is silicosis. To avoid its propagation, companies should take every possible precaution that the working atmosphere is free from dust, abating this by frequent sprinkling of the workings using, wet drills and furnishing the workmen adequate protective apparatus such as respirators.

Jan 1, 1937

By Douglas J. Harvey

The surface tension of lead-tellurium alloys (in the range 0 to 6.70 at. pct Te) ad lead-arsenic alloys (in the range 0 to 10.53 at. pct As) has been examined by the maximum bubble pressure method. The surface tension of high purity lead can be expressed over a range of temperatures (M.P. to 750°C) by the relationship = 512 — 0.133t. Arsenic and lellurium were both found to be surface active in lead. The surface excess concentration at 700°C was .found to be constant at 0.74 x 10-10 moles per sq cm for tellurium. The surface excess of arsenic at 700°C varied between 0.26 x 10-10 moles per sq cm at 0.16 at. pct to 1.5 x 10-10 moles per sq cm at 8.3 at. pet. The surface tension of lead has been investigated sporadically over the last 90 years. The first recorded study was made by Quincke1 who used a rather crude application of the drop-weight method. Hogness2 obtained the first reliable value for the surface tension of lead by measuring the pressure necessary to force the liquid metal from the end of a small capillary of known radius. Hogness gives the empirical formula: ?(surface tension)= 444 - 0.077 (l-327) which describes the relationship between surface tension and temperature ("C); This work was followed by that of Bircumshaw3 who applied the two-capillar maximum bubble pressure method of Sugden.4 The values published by Bircumshaw are in good agreement with those found by Hogness. Matuyama5 examined the surface tension of lead by the drop weight method. However, the values found are somewhat higher than those previously reported. More recent investigations by Greenaway6 and by Melford and oar' have resulted in data which are not in close agreement, but which are well within the expected range at most temperature levels. The study of the surface tension of lead alloys began with Drath and sauerwald8 who examined the lead-bismuth system. They found that the surface tension values of the alloys in this system deviated only slightly from the ideal mixture rule. Matuyarna5 examined the lead-antimony system. Bircumshaw the lead-tin, and the lead-indium system was studied by Hoar and Me1ford.10 The results of these investi- gations are summarized in Fig. 1. It may be seen that the data vary only slightly from the ideal mixture rule. As none of the metals studied and reported in the literature has a very interesting effect on the surface tension of lead,*the next logical step might be to examine the effect of metals of low solubility or nonmetals having some liquid solubility. Baes, and Kellogg11 have pointed out that the elements most likely to be surface active in liquid metals are ones of limited solubility in the liquid state and possessing weak intermolecular bonding forces in the solid state. Therefore, Group V, VI and VII nonmetals are most likely to be surface active. It was decided to examine the effect of a borderline metal, arsenic, and a nonmetal tellurium. Arsenic forms a eutectic with lead having a melting point of 290°C and a composition of 6.9 at. pct As.13 Pure arsenic sublimes when heated above 610°C. Even though alloying with lead lowers the vapor pressure, fumes containing arsenic are evolved at a very noticeable rate when lead-arsenic alloys are heated above 650°C. Tellurium raises the liquidus temperature of lead sharply to 904°C,14 the melting point of PbTe (lead-telluride). The solid solubility of tellurium in lead was determined by Greenwood and worner15 to be 0.0007 at. pct at room temperature. EXPERIMENTAL METHOD Surface Tension Measurement—The two capillary maximum bubble pressure method for measuring surface tension developed by Sugden,4 and used later

Jan 1, 1962

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

By N. Parlee, V. C. Kashyap

The solubilities of nitrogen in liquid iron and liquid Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys were measured by the Sieverts method. Measurements were made at 1600° to 1800°C on binary alloys up to 20 pet Ni, 10 pet V, 10 pet Mo; and on ternary alloys containing 0 to 3 pet V with 0 to 5 pet Mo. The results on liquid iron confirm that Sieverts' law is obeyed in the range 50 to 750 mm pressure. The measured solubilities and their temperature coefficients are in general agreement with other modern authors. The logarithms of the activity coefficients of nitrogen in the binaries are approximately linear functions of the pet of alloying element. A method suggested by Wagner, Chipman, and others for predicting gas solubilities in complex alloys from solubility data on binaries was applied to the Fe-Mo-V alloys. Reasonably good agreement was obtained between calculated and experimental solubilities. NITROGEN'S solubility in liquid iron has been studied by a number of investigators. It is reasonably well established that the solubility of nitrogen follows Sieverts' law at least up to 1 atm partial pressure and that the solubility increases gradually with temperature. The solubility of nitrogen in Fe-X binary liquid systems has been investigated in only a few cases. Only the systems Fe-Cr,3-5, 7 Fe-V,3 Fe-Mn,3, 5 Fe-Ni,3, 5 Fe-Si,B, H Fe-C, L, H and Fe-P4 appear to have received any study. The only work on liquid Fe-V was done by Brick and Creevy.3 This was limited to 13.5 pet and 26.5 pet V, but no exact temperatures were recorded. No work whatsoever appears to have been done on liquid Fe-Mo alloys and even work on Fe-Ni alloys is rather scant. The work on liquid ternary systems is still more limited, and the only publication available appears to be that of Wentrup and Reif,7 who studied the Fe-Cr-Mn and Fe-Cr-Ni alloys. Rassbach, Saunders, and Harbrecht17 have reported work on the solubility of nitrogen in stainless steel but this was not a systematic study of any particular system. Commercial alloys usually contain several alloying elements. Thus, it often becomes important to be able to predict the nitrogen solubility in systems containing two or more added elements without the necessity of making measurements. Wagner,14 Chipman," Darken and Gurry," and Morris and Buehl 14 have suggested means by which this may be accomplished, and Langenberg14 has recently applied one of these methods to nitrogen solubility in complex liquid alloys. This paper reports the results of nitrogen solubility determinations on Fe-Ni, Fe-Mo, Fe-V, and Fe-Mo-V alloys and compares calculated and experimental solubilities in the ternary alloy. Attempted measurements on Fe-Cr alloys were not successful by the experimental method employed. Experimental Method The general method of solubility measurement was that of Sieverts.' The apparatus and procedure were essentially the same as used by Liang, Bever, and Floe."' The equipment consisted of a small vacuum furnace heated by a 6 kw induction unit, gas measuring apparatus, and a gas purification train. The crucibles used were Norton Alundum with alumina sand around them for insulation. The crucibles were charged with 100 to 200 g of material, about 180 g or nearly filling the crucible being found most satisfactory. Hot volumes were determined with argon and ranged from 95 to 130 cu cm (stp). Temperature measurements were made with a Leeds and Northrup optical pyrometer which was calibrated periodically against the melting point of iron in the same apparatus."-'* Good quality nitrogen, hydrogen, and argon gases were further purified and dried in standard purification trains. The sources of the high purity iron and other alloying elements used were as follows:

Jan 1, 1959

By F. N. Rhines, A. S. Nemy

The mode of high-temperature tertiary creep of 523-0 aluminum alloy was found to be strongly stress dependent. The occurrence of necking and/or fissures during tertiary creep exhibited a sequence with varying stress, wherein fissures with no necking occur at a minimum stress and necking with no fissures occur at a maximum stress. At an intermediate stress, tertiary creep begins without necking but with fissures in a region just beneath the external surface, followed by necking and the development of fissures along the axis of the specimen. The results are interpreted in terms of grain boundary gliding and the hydrostatic stresses produced by restraints to grain boundary gliding. THERE appear to be two possible reasons for the existence of a period of accelerating elongation prior to rupture during high-temperature creep in metals; namely, 1) a change in the structure of the metal itself, leading to a change in its response to loading, and 2) a reduction in the cross section of the metal resulting in a higher unit loading. Howe,' by annealing and retesting broken low-temperature creep specimens, found that irreparable damage is done once a metal is subjected to creep. Andrade2 first pointed out the association between the reduction in cross section and the increase in creep rate. The present research was designed to investigate both of these factors by retesting specimens machined from material which had been subjected to high-temperature creep testing short of rupture. EXPERIMENTAL METHOD An aluminum alloy, 52s-0, was selected for these studies because it is constitutionally simple, is strong enough to be relatively insensitive to mechanical damage during machining,3 and undergoes accelerating creep in a convenient temperature range. This alloy is hardened by 2.6 wt pct Mg in solid solution and is not subject to overaging effects; it has a very small quantity of an insoluble impurity phase, Mg2Si, finely dispersed throughout its micro-structure. Creep specimens, similar in design to ASTM 0.252-in. tensile specimens, were machined from 3/4-in. round stock and the surfaces were electro-polished. A 24-hr anneal at 500°C was then applied to stabilize the grain size to an average diameier of 0.27 mm. Subsequent heating for as long as 700 hr at the intended test temperatures produced no change in the tensile properties, indicating a well-stabilized state of the material. Corresponding to each of the typical testing conditions listed in Table I, one creep specimen was tested to destruction and this test was employed as a guide in the selection of times for subsequent tests. Duplicate creep tests were then run to various points along the creep curve to produce specimens which were used to determine changes in mechanical properties and microstructures. The latter were examined at the midsections of the specimens. Other specimens were tested to various stages of tertiary creep, after which they were remachined to new cylindrical test specimens, electropolished and re-tested in creep. RESULTS The major findings of this investigation may be illustrated by a comparison of the results of three sets of creep tests. These were run at 400°C at three stress levels, namely 750, 1000, and 1500 psi. In presenting these results in Figs. 1, 5, and 8, the creep curves are given in pairs: That curve of each pair which is drawn through filled circles corresponds to the initial test, and the curve drawn through open circles (and designated by - R) represents the result of retesting the same specimen after machining to a new cylindrical surface. The load was readjusted to the original unit stress at the beginning of each retest.

Jan 1, 1960

By W. F. Domis, F. von Gemmingen, F. Garofalo

The effect of rain size on the creep behavior of an austenitic iron-base alloy has been studied at 1300° F under conditions of constant stress. The average grain diameter varied between 9 and 190 p (ASTM 10.7-2). The subgrain size and apparent activation energy for creep were not found to depend in any systematic manner on gain size. Grain hozmdary serrations were observed in all specimens tested. The variation of the secondary-creep rate, 2,, with the pain diameter, 1, is given by: es = K(213m + 1 )/l.]; 1, is the grain diameter zohere is reaches a minimum. Results in the literature shoujthat 1,increases as the temperature increases. At low creep temperatures is is therefore proportional to 12, at intermediate temperatures <, exhibits a minimum, and at high creep temperatures is is proportional to 1/1. The dependence ofis on the stress, u, is given by: t, = A" (sinh acrln, a and n show little variation with 1. The dependence of A" on 1 is given by: A" = KA[(21k + 13)/1]. For 1 » >>lmn = 4, and at constant values 01- isat lozu stress levels, the steady-state stress is given by the Hall-Petch relation. The variation of c, with grain size is believed to he associated particularly with grain boundary generation of dislocations which becomes more important with increasing temperatures. SEEMINGLY inconsistent experimental findings have led to a certain amount of confusion concerning the effect of grain size on creep behavior. The confusion is attributed to a lack of test results obtained over sufficiently wide ranges in grain size, stress, and temperature. Experimental results presented in this paper and results available in the literature1-5 show a consistent behavior and lead to a unified concept for the dependence of secondary-or steady-state creep rate on grain size. In accordance with this concept, which is substantiated experimentally, secondary-creep rate should increase with increasing grain diameter at low creep temperatures, leading to greater creep strengths for fine-grained materials. At intermediate temperatures the secondary-creep rate should decrease to a minimum and then increase as the grain size is increased. At high creep temperatures the secondary-creep rate should decrease with increasing grain size, leading to greater creep strengths for coarse-grained materials. Whether a temperature is high or low for creep in a metal or alloy depends primarily on its melting temperature. MATERIAL AND TEST PROCEDURES The material tested was an austenitic iron-base alloy of the following composition (wt pct): C, 0.005; N, 0.017; Mn, 1.26; Ni, 14.21; and Cr, 17.18. Two 15 -lb ingots were forged and hot-rolled to 5/8-in.-diam bars which were then cold-rolled and cold-swaged to a diameter of 0.49 in. These were sectioned into 3-in.-long blanks and heat-treated at various temperatures to obtain different grain sizes. The procedures employed and the results obtained are summarized in Table I. The secondary treatment at 1400° F followed the primary treatment without intermediate cooling to room temperature. This final treatment was employed to minimize various effects arising from heating to different temperatures during the primary treatment, particularly differences in intragranular dislocation structure, segregation of interstitial atoms at grain boundaries, and density of grain boundary ledges. The intragranular dislocation structure was examined by electron transmission metallography after each of the treatments described in Table I. Isolated dislocations and a few tangles were observed but no evidence of subgrains was found after any of the treatments. No grain-size effect was evident on the density and distribution of dislocations. Stabilization of grain boundary structure is particularly important because, as will be discussed later, grain boundaries influence high-temperature creep behavior. Magnetic-permeability measurements after each treatment and

Jan 1, 1964

By H. F. Beardmore

PETROLEUM consumption during 1946 broke all previous records and further increases are expected during 1947. U. S. consumption amounted to an average of 5,280,000 bbl a day, of which 4,745,000 bbl was domestic crude oil, with the rest from natural gasoline production and crude oil imports. World consumption during the past year, excluding Russia, is estimated at 7,200,000 bbl daily. Forecasts for 1947 indicate a U. S. consumption of 5,425,000 bbl daily of petroleum products. This is expected to be made up of 4,655,000 bbl of domestic crude oil production, 340,000 bbl of natural gasoline production, 400,000 bbl of crude oil imports, and the rest from stocks. Petroleum&apos;s principal use is still as a fuel. The field remains highly competitive, but petroleum has been continuously progressing. Less than fifty years ago, oil supplied only one twentieth as much of the nation&apos;s total energy as coal, but today it supplies over half as much.

Jan 1, 1947