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By C. R. St. John, R. W. Lindsay, Charles R. Austin

MANY of the factors influencing the creep behavior of ferrous alloys have been investigated and reported upon in the literature, including such variables as grain size, steelmaking practice, nature and stability of the microstructure, and the effect of alloying elements in steels. However, with respect to the latter, the microstructures involved are usually heterogeneous and as a result the effect of the addition is related to its effects on the various phases present in the microstructure. In the instances where this structure consists of ferrite and carbide, the behavior of the alloy addition will be related to its action in strengthening ferrite and in opposing temperature softening of ferrite as well as coalescence of carbide. The present paper is the third in a series comprising a comprehensive review of investigations on the properties of iron binary alloys. 1.2 Its purpose is to describe the results of isolating one microstructural phase, namely ferrite, and studying its creep characteristics in both the unalloyed and alloyed conditions. This should aid in establishing to a large degree the importance of ferrite in the creep behavior of steels consisting of the previously mentioned ferrite-carbide aggregate. REVIEW OF PREVIOUS WORK In view of the fact that the present investigation deals only with the effects of silicon, manganese, chromium, molybdenum, nickel, and cobalt, and to a certain extent with the effects of carbon, the review of previous literature will be confined to these elements. Practically no references were encountered dealing with the influence of these elements on the creep characteristics of the isolated phase. However, various contributions have dealt with the creep behavior of low-carbon steels alloyed with the elements under consideration. A particularly concise review in this respect is given by Bullens (Battelle)3 and much of this material has been drawn upon. The definite improvement in creep resistance and high-temperature strength conferred by molybdenum is well known. Published suggestions by the A.S.M.E.4 permit of an increase of some 2000 to 5000 lb. per sq. in. in permissible design loads over a temperature range from 650° to 1000°F. as a consequence of additions of 0.40 to o.60 per cent of this element in carbon steels of the order of o.25 to o.35 per cent carbon content. Babcock and Wilcox Tube Co.5 has published data showing the pronounced increase in stress necessary to cause one per cent creep per 10,000 hr. when additions of 0.5 or 1 per cent molybdenum are made to a plain carbon steel. These data apply to temperatures over a range from 800° to 1000°F.

Jan 1, 1945

1938 ABERNATHY, G E Feb 6, 1948 Min & Met Apr 1948 1937 ADAMS, ARMY Aug 20, 1949 Min Eng Dec 1949 1946 ADDY, GEORGE E Sept 24, 1950 Min Eng July 1951 1920 ALDERSON, WILTON P Feb 1951 Min Eng Sept 1952 1896 ALDRICH, T H , JR May 24, 1950 Min Eng Aug 1950 1942 ALDRIDGE, LEONARD June 8, 1952Jrn Met Sept 1952 1919 ALLEN, ROLLAND C July 18, 1948 Min &Met Sept 1948 1950 ANDERSON, C P Unknown Min Eng Feb 1951 1937 ANDERSON, JOHN H May 10, 1950 Min Eng Aug 1950 1914 ANDERSON, L DOUGLASS Unknown Min Eng Nov 1951 1948 ANDRAU, E W K Oct 20, 1951 1936 ANDREWS, CHARLES B Apr 19, 1950 Min Eng June 1950 1918 ARMITAGE, PAUL June 28, 1949 Min Eng Oct 1949 1924 ARMSTRONG, PERCY A E Jan 23, 1949 Min Eng May 1949 1906 ARNOLD, CHARLES LE NEVE Aug 7, 1949 Min Eng Oct 1949 1945 ARNOLD, HAROLD S Aug 7, 1950 Min Eng Oct 1950 1936 ASH, JAMES E Dec 17. 1949 Min Eng Apr 1950

Jan 1, 1952

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.' DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature' giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.' If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson' reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however', for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

ALLERTON S. CUSHMAN, Middletown, Ohio (written discussion*).¬ This subject is one to which I have given much thought and study and which I have frequently discussed informally with Mr. Cain and others. I have long been convinced that the gaseous elements, either combined or entrained (occluded), in steel play a much more important role than is ordinarily admitted. This is probably due to the difficulties encountered in the accurate quantitative estimation of gases, some of which Mr. Cain has referred to, as well as to the fact that, considered from the weight-percentage basis, gas content is measurable only in hundredths or even thousandths of 1 per cent. Volumetrically, however, the results ob-tained by modern research are startling, to say the least. Baraduc-Muller,1 as cited by Mr. Cain, pumped out of 1000-lb. ingots of basic Bessemer steel 2100 l. of gas. or about 75 cu. ft., at normal temperature and pressure, per ton of steel. In other words, we are to understand that Bessemer steel normally carries about fifteen times its own volume of gas. According to Baraduc-Müller's table of results, which is given here-with, carbon monoxide, nitrogen, and hydrogen are important consti-tuents of Bessemer steel, the latter gas being undoubtedly formed by the

Jan 11, 1919

By S. Weissmann, P. R. Swann, D. F. Wriedt

The sizes and density of precipitates in an intemally oxidized 0.19 wt pct Al-Ag single crystal have been determined by low-angle X-ray scattering and by transmission electron microscopy . The correlation in particle sizes measured by the two techniques is reasonably good. For an oxidizing temperature of 800°C the particles were found to INTERNAL oxidation of dilute alloys of aluminum in silver produces an oxide which has an excess of oxygen compared to Al2O3.' It is believed that the excess oxygen is an indication of the small sizes of the oxide particles. Depending upon the particular model chosen for the oxide structure, the size of the o-A1 particles can be calculated as a function of the oxygen-to-aluminum ratio. These calculations pre- have diameters in the range 30 to 140A, with a mean size of about 50.4 as observed by electron microscopy. At lower oxidizing temperatures, less than 600°C, no clearly resolved particles are formed, and it is suspected that if A1-0 clusters exist they must be exceedingly small, i.e., 10A or less in diameter. dicto that the particles would vary in size from 15 to 100A. This range of sizes is amenable to detection by both small-angle X-ray scattering and transmission electron microscopy. This paper compares the cluster sizes in such internally oxidized A1-Ag alloys determined by transmission electron microscopy and small-angle X-ray scattering. SPECIMEN PREPARATION Single crystals were prepared from 99.9999 pct Ag, obtained from Cominco Products, and 99.99 pct Al, obtained from Aluminum Co. of America. All melting operations were carried out in graphite molds under flowing purified hydrogen in a horizontal zone refiner. The silver was first degassed,

Jan 1, 1964

By David B. Reger

The substantial expansion of previously discovered gas pools was the principal feature of petroleum activity in West Virginia during 1940. At least one new gas pool was discovered and various other successful wildcat completions may prove to be gas-pool openers. Some slight extensions of oil pools were also made. The new productive territory, principally gas, added by these extensions was approximately 33,800 acres. ' In general, oil activity was slight because of unfavorable crude prices. Gas activity, on the contrary, increased considerably, although the price of gas did not materially change. The account of operations, as gathered from trade journals and other reporting services, shows that 709 new wells were drilled, resulting in 102 new oil wells with I055 bbl. of daily new produc-tion; 468 new gas wells with 633>g47,000 cu. it. of daily open flow; and 139 dry holes. Also, 91 old wells were drilled to deeper sands, with 143 bbl. and 44,833,000 cu. ft. of added production. On the new wells the oil average was 10.34 bbl, per well per day; and the gas average was 1,354,000 cu. ft. per well per day. On new wells the ratio of dry holes to completions was 19.61 per cent. On deeper drilling to other sands the ratio of failures was 12.I per cent. From an exploratory standpoint, one strictly new gas pool (Lorentz) was opened in Upshur County. Little forecast of its extent or reserve can now be made. The new extensions of various other previously discovered pools, however, give assurance of a new gas reserve that will equal approximately a year of gas demand. In addition to these definite supplies two widely separated Oriskany sand (L. Dev.) wildcats in Jackson County, one of which was completed late in 1940 and the other early in 194.1, may indicate two separate pools or may greatly extend known pools. In south-ern Kanawha County, also, an old Oris-kany-sand well deepened to the White Clinton sand (Sil.) showed a volume of 733,000 cu. ft. and rock pressure of 1800 Ib., giving rather clear assurance that this deep sand, in which only slight quantities of gas had previously been found, should eventually supply much new gas. On the other hand, various deep tests to the Oriskany sand in Harrison, Putnam, Randolph and Wood Counties were totally dry or gave only small volumes of gas, The principal oil wells completed, by counties, were: Calhoun, 15; Clay, Ir; Pleasants, 14; Ritchie, 15; and Roane, 7. Production for the year was estimated by the U. S. Bureau of Mines as 3,444,000 bbl., as compared to 3,684,000 bbl. in 1939. The leading counties in gas-well completions were: Boone, 36; Braxton, 17; Cabell, 25; Calhoun, 16; Clay, 22; Gilm.er, 47; Jackson, 38; Kanatvha, 77; Lincoln, 18; Putnam, 32; IGtchie, 40; and Wayne, 31, Production for the year is estimated by me as I70,000,000,000 cu. ft. as compared to I59,226,000,000 cu. ft.* in 1939. No long pipe lines were built but various gas-line extensions and cross connections,

Jan 1, 1941

By David B. Reger

The substantial expansion of previously discovered gas pools was the principal feature of petroleum activity in West Virginia during 1940. At least one new gas pool was discovered and various other successful wildcat completions may prove to be gas-pool openers. Some slight extensions of oil pools were also made. The new productive territory, principally gas, added by these extensions was approximately 33,800 acres. ' In general, oil activity was slight because of unfavorable crude prices. Gas activity, on the contrary, increased considerably, although the price of gas did not materially change. The account of operations, as gathered from trade journals and other reporting services, shows that 709 new wells were drilled, resulting in 102 new oil wells with I055 bbl. of daily new produc-tion; 468 new gas wells with 633>g47,000 cu. it. of daily open flow; and 139 dry holes. Also, 91 old wells were drilled to deeper sands, with 143 bbl. and 44,833,000 cu. ft. of added production. On the new wells the oil average was 10.34 bbl, per well per day; and the gas average was 1,354,000 cu. ft. per well per day. On new wells the ratio of dry holes to completions was 19.61 per cent. On deeper drilling to other sands the ratio of failures was 12.I per cent. From an exploratory standpoint, one strictly new gas pool (Lorentz) was opened in Upshur County. Little forecast of its extent or reserve can now be made. The new extensions of various other previously discovered pools, however, give assurance of a new gas reserve that will equal approximately a year of gas demand. In addition to these definite supplies two widely separated Oriskany sand (L. Dev.) wildcats in Jackson County, one of which was completed late in 1940 and the other early in 194.1, may indicate two separate pools or may greatly extend known pools. In south-ern Kanawha County, also, an old Oris-kany-sand well deepened to the White Clinton sand (Sil.) showed a volume of 733,000 cu. ft. and rock pressure of 1800 Ib., giving rather clear assurance that this deep sand, in which only slight quantities of gas had previously been found, should eventually supply much new gas. On the other hand, various deep tests to the Oriskany sand in Harrison, Putnam, Randolph and Wood Counties were totally dry or gave only small volumes of gas, The principal oil wells completed, by counties, were: Calhoun, 15; Clay, Ir; Pleasants, 14; Ritchie, 15; and Roane, 7. Production for the year was estimated by the U. S. Bureau of Mines as 3,444,000 bbl., as compared to 3,684,000 bbl. in 1939. The leading counties in gas-well completions were: Boone, 36; Braxton, 17; Cabell, 25; Calhoun, 16; Clay, 22; Gilm.er, 47; Jackson, 38; Kanatvha, 77; Lincoln, 18; Putnam, 32; IGtchie, 40; and Wayne, 31, Production for the year is estimated by me as I70,000,000,000 cu. ft. as compared to I59,226,000,000 cu. ft.* in 1939. No long pipe lines were built but various gas-line extensions and cross connections,

Jan 1, 1941

By M. J. Mullikin, J. B. Conway

Equations capable of representing combined first -and second-stage creep behavior include the Andrade, Cottrell-Aytekin, Garofalo, and de Lacombe equations along with a third-degree polynomial in t1/3. Employing some recent high- temperature creep data for arc-cast tungsten the effectiveness of these expressions was evaluated. It was found that, in this instance, the most accurate representations were afforded by the third-degree polynomial in t1/3 and the de Lacombe equation. Also noted was the fact that the Andrade equation gave results just slightly inferior to those obtained with the third-degree polynomial, definitely better than those due to the Cottrell-Aytekin equation, and slightly superior to those furnished by the Garofalo equation. EXPRESSIONS designed to describe combined first -and second-stage creep behavior must possess certain specific characteristics. At time zero the equation must reduce to a strain value corresponding to the instantaneous deformation on loading. Then in the early moments following load application transient-creep behavior must be described to reflect a creep rate which constantly decreases with time. And finally at larger time values linear (or at least nearly linear) strain-time behavior must be accounted for to yield the steady state or minimum creep rate. Some equations, such as the one based on the parabolic creep law, yield fairly satisfactory results in transient analyses but are not effective at all when combined first- and second-stage data are to be analyzed. Other equations give equally accurate results in both instances although in general the complexity of the equation is slightly increased. For example the Andrade1 equation: has found fairly general application in expressing first-stage creep behavior. Furthermore the contribution of the exponential term becomes more and more prominent as the time increases and causes this equation to exhibit a point of inflection at large values of time. With a proper selection of equation constants the curve can be made fairly flat in the region of the inflection point indicating a desirable equation form for combined first- and second-stage creep analysis. Another equation form with the proper characteristic is that of Cottrell and Aytekin:2 e =a +bt1/3 +ct [2] Obviously as time increases the first derivative of this expression approaches a constant value to suggest application to combined first- and second-stage creep analysis. Similarly a third-degree polynomial in t1/3: e -a + bt1/3 + ct2/3 +dt [3] has the same characteristics. Expressions of this type have been shown3 to be very effective in the analysis of transient-creep behavior and the fact that the first derivative has the same characteristic as Eq. [2] suggests use in the combined analysis.

Jan 1, 1967

By Murray F. Hawkins, W. J. Ainsworth

In all types of subsurface pressure gauges the extension which occurs in the pressure-sensitive element is a function of the difference between the external (well or calibration) pressure and the internal pressure within the gauge, rather than a function of the external pressure only. The internal pressure is near atmospheric and depends upon (a) the quantity of air sealed within the gauge at the time of calibration or measurement, (b) the quantity of moisture (liquid water), if any, sealed within the gauge, and (c) the temperature at which the calibration or well measurement is made. Part of this correction for the change of internal pressure with temperature is taken care of by the customary temperature coefficient of the gauge. However, part of it is not, and while this portion may be only a few psi, it is nevertheless predictable or preventable, and should be considered in precision measurements. ERROR NO. 1 If air is sealed in the gauge at the same temperature and pressure for both the calibration and the well measurements, the usual temperature correction will take care of any difference between calibration and well measurement temperatures. However, if air is sealed within the gauge at temperature T1 and pressure P1 at calibration but at temperature T2 and pressure P2 for a well measurement, because different amounts of air are sealed within the gauge in each case, the internal pressure at. or corrected to, calibration temperature Tr will he different by where all temperatures and pressures are absolute. The calibration temperature is used, and not the well measurement temperature, because the usual temperature correction reduces the well measurements to calibration temperature. The correction term as calculated by the above equation is separate from. and in addition to, the usual temperature correction. Example: T, = 540°R, sealing temperature at calibration P, = 14.7 psia, sealing pressure at calibration T2 = 460°R, sealing temperature at well P2 = 14.7 psia, sealing pressure at well Tr = 660°R, calibration temperature AP = 660 [14.7/460 — 14.7/540] = 3.1 psi While this error is small even under these somewhat maximal conditions, it nevertheless represents a practical situation which did occur, and which as a matter of fact gave rise to this note. Where AP is positive, as above, the correction is added to the measured pressure; where negative, subtracted from the measured pressure. This correction should also be considered in successive calibration runs where the gauge, for example, may be warm from a previous calibration at an elevated temperature. ERROR NO. 2 Where a small quantity of moisture (liquid water) is sealed within the gauge at atmospheric conditions, the increased vapor pressure of the water at higher well or calibration temperatures will cause an increase in internal pressure. This moisture will come presumably from condensation within the gauge following temperature changes, from moisture on the operator's hands, and from atmospheric moisture (rain, mist, fog, etc.). Calculation shows that approximately 0.2 cc of water (three to four drops) is sufficient to saturate the air within an Amerada RPG-3 Gauge at 160°F, at which temperature the vapor pressure of water is about 5 psia. As the vaporization occurs in a sealed volume, the increase in internal pressure will be in excess of this 5 psi. At higher temperatures the pressures will be higher; however more water will be required to saturate the air within the gauge. Some experimental work was carried out with an Amerada RPG-3 Gauge at 200°F fitted with a 1,000 psi element, both with a dry recording chamber and with a small amount of water added. The results directly proved the existence of the error due to the presence of moisture, and, it is felt, indirectly, due to the differences in sealing temperatures and pressures, as both effects may be ascribed simply to an increase in the moles of gas within the recording chamber. SUMMARY In precision measurements the error introduced by sealing the gauge during a well test at a different temperature and pressure from that of calibration may be corrected for by using the equation presented, or it may be prevented by taking care always to seal the gauge at near calibration conditions. The error introduced by sealing moisture in the gauge may be prevented by taking care to keep moisture out of the gauge, or by removing the moisture by either warming or evacuating the gauge. Both of these errors are independent of the range of pressure measurement and the type of gauge, and are in addition to the usual temperature correction. ACKNOWLEDGMENT Appreciation is expressed to W. B. Kendall, Geophysical Research Corp., Tulsa, Okla., who pointed out the error from differences in sealing temperatures during some winter work in Canada. ***

Jan 1, 1956

By K. G. Davis

Dilute alloys of silver and of thallium in tin have been solidijzed unidirectionally under controlled conditions, to study the segregation associated with a cellular interface under conditions where both thermal and solute convection are present. Autoradiography and radioactive tracer counting techniques were combined with electron-probe microanalysis to study both macro- and microsegregation. It was found that, for concentrations giving only small amounts of constitutional supercooling, cell formation had little effect on the macroscopic distribution of solute along the specimen. At higher concentrations the effective distribution coefficient was higher than that expected for a smooth interface. Node spacing was independent of initial solute content at lower concentrations, becoming greater as keff increased. Silver content at the segregation nodes of silver in tin alloys was independent of initial concentration and considerably in excess of the eutectic composition. SINCE the investigation of cell formation at advancing solid-liquid interfaces by Rutter and Chalmers,' a large volume of work has been dedicated to the determination of solidification conditions under which a planar interface will break down into cellular form. Early experiments were explained satisfactorily by the concept of constitutional supercooling,2 but, due to poor measurement of temperature gradients in the liquid, lack of accurate data on liquid diffusion and equilibrium distribution coefficients, and uncertainty about the effects of thermal and solute convection, these experiments cannot be used as proof for the theory. More recent work, however, has shown that under conditions where convection is eliminated or can be ignored good correlation is observed.3,4 Investigations into segregation at cell caps5 and at cell nodes6-'' have been made, but no measurements appear to have been done on the overall, macroscopic segregation down a unidirectionally solidified rod of material which has solidified with a cellular substructure. This has practical importance in casting, where regions of material with cellular substructure are often encountered, and also in zone refining where the thermal conditions necessary for a planar interface are unattainable. Further, as will be shown, the macroscopic segregation can give information on the following question. Granted that a cellular solid-liquid interface develops from a planar one when the conditions for constitutional supercooling are exceeded, how much supercooling is present after the cells have formed? EXPERIMENTAL PROCEDURE AND RESULTS Specimen Preparation. Specimens 25 cm long with a square cross section 0.6 by 0.6 cm were grown in graphite boats by solidification from one end. Alloy compositions are given in Table I. Two specimens of each composition were grown. The tin was 5-9 grade and the silver and thallium both 4-9 grade. Ag110 and Tl204 were used as tracers. Each composition had the same quantity of tracer so that auto radiographs of specimens containing different concentrations of the same element could be easily compared. Thermocouples inserted through the lid of the boat into a dummy specimen showed that, over the first 10 cm of growth, thermal conditions were quite steady, with a rate of interface advance of 5.8 cm per hr and a temperature gradient in the melt ahead of the interface of 3.0°C per cm. The specimens were seeded from tin crystals of a common orientation to eliminate orientation effects. Dilution of the specimen by seed material was minimized by the provision of a narrow neck between specimen and seed crystal. Macrosegregation. After growth, the specimens were sectioned with a spark cutter. The rods of silver alloy were cut into 1-cm lengths and analyzed for Ag110 using a y -ray counter with fixed geometry. The specimens containing thallium were cut into 2-cm lengths and analyzed for T1 204 by taking 13 counts from each end of the cut lengths through an aperture in lead sheet approximately 0.4 cm square. The results are summarized in Figs. 1 and 2. To find the effective distribution coefficient for the silver in tin alloys under smooth interface conditions, the region of substructure at the bottom surface of one of the 10 ppm specimens, see Fig. 3, was removed by spark machining before counting. Autoradiography. For both alloy systems the samples were polished on sections taken alternately parallel and perpendicular to the growth direction, and autoradiographed by placing the polished surfaces in contact with Kodak "Process Ortho" film. Figs. 3 and 4 show the structures revealed. The alloy containing 10 ppm Ag showed substructure only after a few centimeters of growth, and then substructure was limited to a narrow layer at the base. The "speckled" substructure reported previously in this system4 is here clearly seen to be an intermediate stage between planar and cellular interface conditions. The other samples show a remarkable similarity considering

Jan 1, 1969

By Alden B. Greninger, Alexander R. Troiano

THE crystallographic mechanism for the austenite-to-martensite transformation has been deduced from the results of the following new experimental determinations: (I) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite-and thus the relationship between the martensite lattice and the martensite plate, and (2) the measurement and analysis of the change in positions that a volume of austenite undergoes when it transforms into a crystal of martensite. For the latter study, a new tool was developed, the stereographic analysis of shear. Lattice relationship.-Thirty-five separate 50-gram melts of an alloy containing about 22 per cent nickel and 0.8 per cent carbon were prepared in a high-vacuum furnace. This alloy is all-austenite at room temperature; grain size was about I cm. Specimens of the alloy were cooled to about -70°C. to form a few martensite crystals, and suitable specimens were ground and polished on a surface parallel to a single martensite plate, exposing the martensite crystal for an area of I mm. or more. Four martensite cystals from four different ingots were prepared in this manner; the largest crystal of this group is illustrated in Fig. I. Back-reflection Lane patterns were obtained from martensite [ ] crystals (and the matrix austenite) both before and after tempering. The locations of the basal-plane pole of martensite was checked by means of oscillating crystal X-ray patterns. All four crystals studied yielded the same solution (±0.5°), and these relationships are expressed in gnomonic projection in Fig. 3.* The narrow dark-etching bands often visible in martensite "needles" were found to be parallel to {112} and thus are undoubtedly twin bands in the martensite crystal.

Jan 1, 1941

By J. F. Nicholas

THE angles between the crystallographic planes in cubic metals were originally given by Bozorth and have been republished many times. Recently, Salkovitz2 tabulated the angles for the hexagonal metals (magnesium, zinc, and cadmium). he most commonly used metal which does not fail into either of these groups is tin, which has a tetragonal structure with an axial ratio of c/a = 0.54558 (99.99 pct purity, 25°C).² ccordingly, Table I has been prepared giving the possible values for the angle, 4, between planes of the types {HKL) and {hkl). The formula used was: Hh + Kk + LI — cos? = —--------------—-----------— A [(H2 + K2 + L2-a2c2(h2 + k2 + r;)] All angles are given correct to the nearest minute as this is sufficient for all practical purposes. Every angle depends in a different way on variations in the value of c/a, but even in the worst cases a variation of about 0.0003 in this ratio is needed to vary an angle by l', which corresponds to a temperature change of 20 °C or can be caused by impurities.

Jan 1, 1952

By E. A. H. Tays

As I promised, in a former paper on the Bryan Mill,* to give further data regarding the plates from four battery-aprons, I now submit the following: These aprons were 4.5 feet wide by 16 feet long; the first two plates of each apron were 4.5 by 4.5 feet, and the remainder of varying sizes, as can be seen by their relative weights, as shown in the table; but all were 54 inches wide. They were in use 4 years and 9 months, and about 15,265 tons of ore passed over each. The ore was quartz, carrying about the same weight in silver as in gold; showing some copper, and highly impregnated with ferric oxide. The tailings show about 0.6 per cent., and the bullion about 10 per cent., of copper. The silver was present mostly as sulphide; and the copper was also present as sulphide, with some carbonate. The ore treated ill 1898 was a fair average of the whole run; so I take it as an example from which to make a few deductions.

Jan 1, 1901

FROM north to south activity is picking up through- out the Labrador Trough-already shown to be one of the world's great iron ore provinces. Center of current activity and interest lies in the mid-southern part of the trough as drills, equipment, and . . . money start to pour into the area near Mt. Wright and Wabush Lake. First major announcement in the area came early this spring when J&L and CCI outlined an estimated billion-ton deposit for "future" operations. Later impetus came from rumored railway for US Steel's Quebec Cartier projects in the Mt. Reed area slightly to the south. As this issue went to press US Steel's request for bids on railway and hydroelectric construction, plus IOCC's decision to step up the time- table on its program in the Wabush Lake area east of Mt. Wright, triggered a flurry of other announcements involving many of the top U. S. and Canadian iron ore firms. Do not look for most of these place names in the average atlas . . . they aren't there yet, but they soon will be.

Jan 6, 1958

By William D. Southard, Joseph W. Schlitt, Bruce P. Ream, Lawrence J. Haug

The operation of Kennecott 's Bingham Canyon copper precipitation plant, one of the world's largest, is described. This description includes a brief historical review of precipitation at Bingham and the general layout and operation of the present cone cementation facility. Current practices are based on results of studies undertaken to define improvements needed in each unit operation. These improvements were required to meet changing plant conditions and were implemented primarily within the constraints of the existing facilities. Specific unit operations included were the cone precipitators, the cone discharge thickener, the cone effluent settling basins, and the plate and frame filter presses. As a result of these improvements, loss of precipitated copper decreased and the degree of precipitation increased, raising copper recovery by 9 t/d. At the same time, iron consumption was reduced by 22.5 t/d. Problems in drying the cement copper were also overcome so that a product containing 12-15% moisture could be consistently delivered for smelting.

Jan 1, 1980

By W. Joseph Schlitt, William D. Southard, Bruce P. Ream, Lawrence J. Haug

The operation of Kennecott's Bingham Canyon copper precipitation plant, one of the world's largest, is described. This description includes a brief historical review of precipitation at Bingham and the general layout and operation of the present cone cementation facility. Current practices are based on results of studies undertaken to define improvements needed in each unit operation. These improvements were required to meet changing plant conditions and were implemented primarily within the constraints of the existing facilities. Specific unit operations included were the cone precipitators, the cone discharge thickener, the cone effluent settling basins, and the plate and frame filter presses. As a result of these improvements, loss of precipitated copper decreased and the degree of precipitation increased, raising copper recovery by 9 t/d. At the same time, iron consumption was reduced by 22.5 t/d. Problems in drying the cement copper were also overcome so that a product containing 12 - 15% moisture could be consistently delivered for smelting.

Jan 6, 1979

By Nicholas J. Grant, Michio Yamazaki

Cast copper alloys containing 10, 20, and 30 pct Ni and 0.75 to 0.80 pct Al were machine-milled into chips, then comminuted in a rod mill to fine flake powder utilizing a number of processing variables. The powders here internally oxidized, mostly at 800°C, in a low-pressure oxygen atmosphere. The consolidated powders were hot-extruded into bar stock. Room-tenmperature tension tests, stress-rupture tests mostly at 650°C, but also at 450° and 850°C, and hardness measurements after various annealing temperature treatments to study alloy stability were perfomted. Excellent room-temperature strength, high rupture strength at 650°C, and resistance to recrystallization at 1050°C were obtained. Problems in optimizing conditions for internal oxidation of Cu-Ni base alloys are discussed. THE interesting high-temperature properties of SAP' have stimulated considerable effort in the study of more refractory alloy systems where the potential for high-strength alloys at high temperature is great.2-13 A number of methods have been utilized to produce the desired fine, hard particle dispersions, of which internal oxidation2,9,7 of dilute solid-solution systems offers considerable promise by virtue of the potential for producing ultrafine, well-dispersed oxides. While most of the published works are concerned with pure metal matrices, a number of investigators have studied the effects of solid-solution strengthening.10,19 Use of more complex alloy matrices (for example, aging systems) has been unsuccessful because overaging still occurs at high temperatures in the oxide-containing alloys.14.15 Solid-solution strengthening is, however, effective at very high temperatures9,10 and might be expected to contribute importantly to the strength of oxide-dispersion strengthened alloys. For this study, internal oxidation of solid-solution alloys of copper and nickel, containing small amounts of aluminum, was chosen as the method of alloy preparation. PREPARATION OF ALLOYS Three copper alloys containing about 10, 20, and 30 pct Ni and each containing 0.75 to 0.80 pct A1 (enough to yield about 3.5 vol pct alumina) were prepared as air-cast ingots measuring 2.5 in. diameter by 6 in. high (see Table I for the analyses). Processing steps for all the alloys were as follows (also see Table 11): 1) Homogenization of the ingot at 982°C (1800°F) for 45 hr in an argon atmosphere. 2) Machine milling of ingots into fine chips. Average thickness was about 0.1 to 0.2 mm. 3) Hydrogen reduction of chips at 593°C (1100° F) for 1 hr to reduce copper and nickel oxides. 4) Rod milling of chips to finer powders. 5) Hydrogen treatment of powders as in step 3. 6) Internal oxidation of the powders. 7) Hydrogen treatment of oxidized powders as in step 3. 8) Hydrostatic compression of evacuated powders. 9) Sintering of compacts in hydrogen. 10) Hot extrusion. Variations in processing among the alloys were made in steps 4, 5, and 10 (see Table 11). In the past, two methods were utilized to internally oxidize alloy powders. Preston and Grant3 surface-oxidized dilute Cu-Al powders to obtain the necessary amount of oxygen to oxidize the solute metal (aluminum and silicon), and then permitted the formed copper oxide to diffuse and react with the solute in an argon atmosphere. Bonis and Grant4 exposed Ni-A1 and other nickel alloys to an oxygen pressure derived from the decomposition of nickel oxide at a preselected temperature, in an argon atmosphere. Both methods are applicable and can be modified to generate a range of oxygen pressures for oxidation of the solute but not the solvent metals. Procedure I: Surface Oxidation of Alloy A3, Cu-10Ni-0.76A1. Powders of -20 to +28 mesh were surface-oxidized at 500°C (932°F) to obtain the desired amount of oxygen for oxidation of the aluminum to alumina; the powder was then sealed in Vycor and heated at 900°C (1652°F) for various times up to

Jan 1, 1965

By R. E. Carter, C. Wagner, F. D. Richardson

By means of inert markers of radio-platinum, it has been shown that cobalt metal oxidizes by out-ward diffusion of cobalt atoms through the oxide. Oxidation rates have been measured at various temperatures and oxygen pressures and have been found to agree with the rates calculated from the Wagner equation and the authors' values for the diffusion coefficient of cobalt in the oxide. The distribution of radio-cobalt in growing oxide loyers has been accurately measured and found to be different from that predicted from the Wagner oxidation theory. Attempts have been made to measure the change of lattice parameter of the oxide with composition. SEVERAL investigators have shown that cobalt metal oxidizes according to the parabolic law,1-3 but no detailed study has been made of the oxidation mechanism. Cobaltous oxide has a metal-deficient lattice, but the defect concentration which is dependent on the oxygen pressure is only approximately known.' From the similarities in the structures of "CoO" and "FeO" and the rate laws governing the oxidation of cobalt and iron, Gulbransen- as suggested that cobalt, like iron," oxidizes by diffusion of cobaltous ions through the oxide layer. To substantiate this hypothesis, he has attempted to measure the oxidation rate of cobalt as a function of the oxygen pressure but has been able to report only that the rate depends on a "small" power of the pressure. On the other hand, Preece," Valensi,' and Arkharov' all have suggested from indirect evidence that oxygen diffuses through the COO to the metal-oxide interface. The present authors, in a previous paper,' have shown that the rate of diffusion of cobalt in cobaltous oxide is dependent on the oxygen pressure. In that investigation, they also found that cobaltous oxide disks made by complete oxidation of cobalt metal were porous at their centers (Fig. 5L, ref. 4). Both these facts strongly suggest that oxidation of the metal proceeds via outward diffusion of cations. In order to establish the mechanism unequivocally, oxidation experiments were made with inert radioactive platinum markers, and the dependence of oxidation rate on oxygen pressure was measured. In addition, an attempt was made to determine the form of the cation vacancy gradient, which the marker experiment showed must exist across a growing oxide layer. This was done by depositing radioactive Co on the surface of a cobalt disk and then measuring the tracer distribution across the oxide layer produced by partial oxidation of the metal. Finally, an X-ray examination was made in an attempt to find the expected change of lattice parameter of COO with oxygen pressure. Experimental The apparatus and materials used were substantially the same as those previously described by the authors.4 Marker Studies: The use of inert markers to follow oxidation reactions was first attempted by Pfeil" in 1929, and radioactive markers have recently been used by Davies et al.' In the investigation reported here, the markers were applied as an (NH4)2PtCI6 slurry in several thin streaks across both faces of four disks of cobalt metal 1 mm thick and 14 mm in diameter. The disks were then oxidized almost to completion at 1200°C in pure oxygen. After oxidation, they were mounted and sectioned and auto-radiographs were taken to locate the markers. Oxidation Rate: The oxidation rate of cobalt was measured at 1148°C at oxygen pressures ranging from 0.0055 to 1.0 atm and at 1000°, 1148", and 1350°C under 1 atm of oxygen. The rate was deter-

Jan 1, 1956

AlFred JamEs," London, Eug.:—I thank you, gentlemen, for Sour kind invitation to address you. It is a very great pleasure for me to be here at your annual meeting, and, although I have been a member since 1894, this is the first opportunity I have

Jan 1, 1909