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YEAR OF ELECTION 1913. FRANK DAWSON ADAMS, Montreal, Canada. 1938. HENRY CORT HAROLD CARPENTER, London England 1933. KARL EIKERS New York, N. Y. 1922. FEDERICO GIOLITTI Torino, Italy. 1906. SIR ROBERT A. HADFIELD London, England. 1921. FRANK WILLIAM HARBORD London, England. 1917. HERBERT HOOVER Washington, D. C. 1931. WALDEMAR LINDGREN Cambridge, Mass. 1921. C. McDERMID London, England. 1913. EZEQUIEL ORDONEZ Mexico City, Mexico. 1935. ROBERT PEELE New York, N. Y. 1938. A.M. PORTEVIN Paris France 1937. JOHN V.W. REYNDERS, New York, N. Y. 1937. GEORGE S. RICE Washington, D. C. 1911. ROBERT H. RICHARDS Cambridge, Mass. 1934. T.A. RICKARD Victoria, B.C., Canada

Jan 1, 1939

The October meeting of the Mining and Geological Society, Lehigh University, was held in the Eckley B. Coxe Mining Laboratory, and was called to order at 8:15 p. m., by President R. L. McCann. After the reading of the minutes of the previous meeting, a short business session was held, for the purpose of electing a Vice-President to succeed G. S. Borden, who has left college. Nominees for the office were: H. J. Sloman, P. S. Justice, L. Sargeant. Dr. F. F. Hintze, of the Geology Department, was elected a member of the Advisory Committee, which now consists of the President-

Jan 12, 1916

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during the period Apr. 10 to May 10, 1915: William W. Elmer, Tuttletown, Cal. R. R. Freeman, Jr., Wollaston, Mass. Lawrence Addicks, Douglas, Ariz. Francis R. Pyne, Elizabeth, N. J. W. F. Durand, Stanford Univ., Cal. George B. Pickett, Ophir, Colo. S. P. Cooper, New York, N. Y. R. V. Norris has been elected President of the Columbia School of Mines Alumni Association. Robert C. Sticht has been elected President of the Australian Insti¬tute of Mining Engineers.

Jan 6, 1915

By R. G. Johnson

The prevailing system of locating wells on a rectangular basis, as shown in Fig. 1-A, has developed because of the exigencies of offsetting at boundary lines. When, however, a very large tract is being drilled, it is often possible to abandon this inferior method for the superior arrange- ment known as "staggering," which is illustrated in Fig. 1, B and C. The advantages of the triangular over the rectangular method are evident from Fig. 2, computed on the basis of one well to 10 acres (4 ha.). With the triangular system, no land is more than 409.4 ft. (124.8 m.) from a

Jan 1, 1920

New York Meets first Wednesday after first Tuesday of each month. DAVID 11. BROWNE, Chairman. JOHN H. JANEWAY, Vice-Chairman. F. E. PIERCE, Secretary, 35 Nassau St., New York, N. Y. P. A. MOSMAN, Treasurer. LEWIS W. FRANCIS. BENJAMIN B. LAWRENCE. Boston Meets first Monday of each winter month. HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. HENRY A. WENTWORTH, Secretary-Treasurer, 60 India St., Boston, Mass. A. H. EUSTIS, F. G. STANTIAL. Columbia Holds four sessions during year. Annual meeting in September or October. STANLY A. EASTON, Chairman. FREDERIC KEFFER, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane. Wash. D. C. LIVINGSTON. FRANK A. ROSS.

Jan 4, 1916

By P. E. Landolt

MILITARY necessities and economic scarcities, occasioned by the first and second World Wars, led to the search for substitute materials and new products to meet the demands of advancing technology accelerated by research development. Among others, lithium came to attention. Its chemistry had been studied for a long period, but its general use was quite restricted due to limited known sources of raw material. In World War I, Germany used lithium metallurgically for two principal purposes: 1-hardened lead alloy, B-Metal, for railway bearings as a substitute for lead-tin-antimony alloys; and 2-light strong aluminum alloys, Scleron, in which zinc was largely substituted for copper.

Jan 12, 1951

C. M. Kay, Chairman L. W. Moore, Post Chairman C. W. Conn, Vice-Chairman R. W. Shearman, Secretary-Treasurer BLAST FURNACE, COKE OVEN, AND RAW MATERIALS COMMITTEE F. C. Anderko, Chairman James Chisholm, Past Chairman W. F. Huntley, Senior Vice-Chairman W. O. Bishop, Vice-Chairman R. W. Shearman, Treasurer D. C. Brown, Secretary IRON AND STEEL DIVISION Gerhard Derge, Chairman J. J. Golden, Past Chairman B. M. Larsen, Chairman-Elect R. W. Shearman, Secretary-Treasurer THE METALLURGICAL SOCIEN OF AIME J. S. Smart, Jr., President C. C. Long, Past President K. L. Fetters, Vice-President T. D. Jones, Treasurer R. W. Shearman, Secretary

Jan 1, 1961

By B. M. Larsen

Attempting to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic" and "macroscopic," depending on whether the variations in concentration of solutes or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also untlerly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all sepregation effects. Undercooling and Nuclei Formation It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus temperature. In practical terms this means that the nuclei number illcreases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. Temperature Gradients and Heat Dissipation during Freezing Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period. Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1945

By B. M. Larsen

ATTEMPTING to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic " and " macroscopic," depending on whether the variations in concentration of solutes? or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also underly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all segregation effects. UNDERCOOLING AND NUCLEI FORMATION It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus tempera¬ture. In practical terms this means that the nuclei number increases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. TEMPERATURE GRADIENTS AND HEAT DISSIPATION DURING FREEZING Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period: Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1944

By Irwin Roman

IN studying the possibilities of a continuously recording magnetometer for use along the surface of the earth and in an airplane, the Federal Bureau of Mines was led to a study of the theoretical resolving power of magnetic observations, both in the variation of the total magnetic intensity and in each of the two components ordinarily measured. Along with this general study, an attempt was made to determine the relative worth of the total intensity anomaly and the vertical anomaly in geophysical prospecting. General considerations led to three conclusions: I. In the northern magnetic hemisphere of the earth, the total intensity anomaly is offset to the south of the vertical anomaly, for a positive anomaly (see Appendix, note I). 2. The resolving power of magnetic observations decreases rapidly with distance from the disturbing body. 3. The horizontal anomaly has little value in prediction of the disturbing body but might be useful in making a choice between bodies suggested by the vertical or total anomaly. Some of the considerations leading to these conclusions were: I. The normal intensity and the anomalous intensity are vectorially additive; hence for a positive anomaly in the northern magnetic hemisphere the total intensity will be a maximum at some point south of the disturbing body and north of the point at which the line to the disturbing body is parallel to the normal earth's field. The anomaly itself has a maximum value directly above the body. For a positive anomaly of constant magnitude, the total intensity will be a maximum when the anomaly vector is parallel to the normal vector. This is shown schematically in Fig. I (not to scale) for a magnetic distribution not restricted to a relatively thin sheet in the magnetic meridian. The normal field has a magnitude Io with vertical component Vo and horizontal component H,. Six station points along a traverse' across the body from south to north are shown at M to S. At each of these stations the normal magnetic field vector terminates at F. At each of these stations the magnetic field vector due to the disturbing body B terminates at A. The line through the station point and the point A passes through B. The magnitude of the anomaly, indicated by the length of the vector terminating at A, is proportional to some power of the distance from the station point to the disturbing body. If the' disturbing body B is a concentrated point of magnetic material, the anomaly is proportional to the inverse second power of the distance. For a uniform magnetic distribution over a line perpendicular to the observed traverse, the anomaly is proportional to the inverse first power of the distance. For surface distributions, the law of intensity is more complicated. At each field point, the total magnetic intensity T is the vector sum of the

Jan 1, 1946

By D. B. Masson

THE martensitic transformations occurring in ,B AgCd as a result of cold working at room temp.. a-ture and cooling below room ten1erature have been reported by Masson and Barrett.1 These authors found that simple cooling to 127°K caused body-cen-tered-cubic AgCd containing 53.0 at. pct Ag to transform to an orthorhombic structure, while mechanical deformation at room temperature was found to induce a hexagonal structure. Furthermore, they observed that the temperature at which martensite first appeared on cooling, Ms, and that at which the transformation was complete, MI, as well as the corresponding temperatures for the reversion on heating, As and Af, could be ascertained to ± 1°K, although they report these temperatures only for the alloy containing 53.0 at. pct Ag (51.96 wt pct). In the work reported here the temperature range of the transformation on cooling was studied as a function of composition, and further consideration was given to the relationship between the original bcc structure and the transformation-induced hexagonal and orthorhomic structures. EXPERIMENTAL PROCEDURE All samples studied were in the form of annealed 300-mesh powder and were prepared from the constituent metals in the manner described previously.1 The compositions in weight and atomic pct are listed in Columns 1 and 2 of Table I. Method of determination of transformation temperature was the same as utilized previously1—measurement of the intensity of X-rays diffracted by the transformation product. A diagram of the low-temperature sample mount is shown in Fig. 1. This mount was made to fit a GE model XRD-3 X-ray diffraction unit. The powder sample was varnished to a flat surface on a copper sample holder at A. This sample holder was soldered to a brass rod, B, which was in turn soldered to a second copper rod, C. Rod C could be cooled to 78°K by inserting it into a reservoir of liquid nitrogen, D. A heater coil of nichrome wire was wound at E on the sample holder, and by varying the current through the heater a thermal gradient could be maintained along brass rod B. Sample temperatures from 78°K up could be attained and held as long as needed. The sample holder and nitrogen reservoir were insulated by Styrofoam, F, and the sample itself was protected by two radiation shields, G. The X-ray beam entered and left the sample chamber through windoys in the supporting container at H and I. Sample temperatures were measured by a calibrated copper-constantan thermocouple varnished to the sample holder just out of the beam at A. The low-temperature structure had been found to possess orthorhombic symmetry1 and the expected positions of the diffraction maxima were known. Therefore the sample was aligned in the X-ray beam and the Geiger counter of the spectrometer set to receive the most intense orthorhombic reflection without an adjacent interfering cubic reflection. This

Jan 1, 1961

By E. V. Potter, H. C. Lukens

In general, during all electrowinning processes, large volumes of gas are liberated at the cathodes of the electrolytic cells. Most of this gas escapes from the electrolyte, but much of it may be absorbed or entrapped in the metal being plated. In many cases, this is not objectionable, but since it is liberated when the metal is heated, it is a potential source of trouble where the metal has to be heated or melted. Since this gas is principally hydrogen, in escaping from a melt it may cause minor explosions and scattering of the molten metal, while in other cases it has been reported to make the metal rise in the molds when cast. Therefore such metals would be more generally useful if all or most of the gas were removed before they were used. In an earlier investigation1 the gas content of electrolytic manganese was determined and methods found for removing most of it without detrimentally affecting the properties of the metal. In this paper results of a similar investigation on electrolytic chromium are presented. Apparatus The apparatus used in these investigations is essentially the same as that used in the manganese work1 and is shown in Fig I. It consists of sample chamber A, vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The pressure in the system is measured by the mercury manometer B. Changes in gas volume are measured by volume gauge C which is essentially another mercury manometer in which the volume of the mercury column is large and can be varied by raising or lowering the well H. In this apparatus the tube had a volume of 100 cc for a 60 cm length. Larger changes in gas volume can be accommodated by auxiliary containers attached to the system at F. The sample is heated by furnace G, the temperature of which is regulated within 5°C by an automatic controller. The only change in the apparatus was the sample container which was made smaller because of the chromium metal's containing more gas than the manganese metal and a smaller sample was used. Method The measurements were made as follows: The complete system when cold was evacuated and refilled with H2 until all the air was removed. It was then refilled with H2 to the desired pressure, as indicated on manometer B. The temperature was then raised to the desired value and as gas was either liberated from or absorbed by the sample, the height of well H was changed to alter the volume of the system so as to keep the pressure constant. In determining rates of liberation of gas, volume readings were taken at convenient tirne intervals depending on the rapidity with which the gas was liberated. In determining total volumes, the specimen was held at constant temperature and pressure until

Jan 1, 1949

By R. W. Guard, M. E. Fine

By treating the dislocation like a surface and ap-plying the usual thermodynamic treatment to the adsorption process a Gibbs adsorption equation for dislocations was derived. For extended dislocations in binary solutions the adsorbed concentration on the fault, X2a, may be computed from (jo/da2b) where a2b is the activity of the solute in the bulk material and s is the stacking-fault energy. Using the data of Howie and Swann for s the adsorption concentration goes through a maximum at 2 at. pct Al in Ag-Al, 10 at. pct Zn in Cu-Zn, and 8 at. pct A1 in Cu-Al. The pinning stress calculated from this concentration difference goes Ihrough a maximum at the same concentration us the peak in X2 a. The computed pinning stress thus does not vary with composition in the manner predicted by Suzuki, as was also pointed out by Hendrickson. The results are compared with the stress increment which can be attributed to Suzuki locking in Cu-Zn and Cu-Al stress-strain curves. They both agree in magnitude and in the location of the maximum. The predicted and observed maximum values for the Cu-Zn system (where activity data are available) are 700 g per sq mm (predicted) and 1000 g per sq mm (measured, laking into account the orientation factor of 2.2 to convert poly-crystalline to single-crystal data). CERTAIN simple internal surfaces may be regarded as dislocation grids. This fact suggested that it might be profitable to consider certain phenomena related to segregation of solute atoms at dislocations from the point of view of the thermodynamics of surfaces and surface adsorption. A general treatment of this type is given and then the results are applied to Suzuki segregation and pinning. Confirmation of the results is obtained from comparison of stress-strain behavior for copper and copper-base alloys. Two kinds of dislocations need be treated: perfect and extended dislocations. In either case the line tension of a dislocation, ?. the work which must be done to increase the length of dislocation by a unit length, is analogous to the surface tension. For an undissociated dislocation ? is the self-energy of a unit length of dislocation; for an extended dislocation where is the self-energy per unit length of a pair of partials far enough apart so that there is no interaction energy, is the interaction energy per unit length, is the stacking fault energy per unit area, and w is the equilibrium separation of the paired partials. In the absence of an applied stress the force pushing the dislocation partials apart in a close-packed structure is Gb2/12p where G is the shear modulus, b is the Burgers' vector of the complete dislocation, and is the separation of the partials. At the equilibrium separation, w this force equals s. Thus

Jan 1, 1965

By E. V. Potter, H. C. Lukens

INTRODUCTION IN general, during all electrowinning processes, large volumes of gas are liberated at the cathodes of the electrolytic cells. Most of this gas escapes from the electrolyte, but much of it may be absorbed or entrapped in the metal being plated. In many cases, this is not objectionable, but since it is liberated when the metal is heated, it is a potential source of trouble where the metal has to be heated or melted. Since this gas is principally hydrogen, in escaping from a melt it may cause minor explosions and scattering of the molten metal, while in other cases it has been reported to make the metal rise in the molds when cast. Therefore such metals would be more generally useful if all or most of the gas were removed before they were used. In an earlier investigation' the gas content of electrolytic manganese was determined and methods found for removing most of it without detrimentally affecting the properties of the metal. In this paper results of a similar investigation on electrolytic chromium are presented. APPARATUS The apparatus used in these investigations is essentially the same as that used in the manganese work' and is shown in Fig I. It consists of sample chamber A, vacuum or pressure gauge B, volume gauge C, vacuum pump D, hydrogen container E, auxiliary gas chamber F, and furnace G. The pressure in the system is measured by the mercury manometer B. Changes in ' gas volume are measured by volume gauge C which is essentially another mercury manometer in which . the volume of the mercury column is large and can be varied by raising or lowering the well H. In this apparatus the tube had a volume of 100 cc for a 61 cm length. Larger changes in gas volume can be accommodated by auxiliary containers attached to the system at F. The sample is heated by furnace G, the temperature of which is regulated within ± 5°C by an automatic controller. The only change in the apparatus was the sample container which was made smaller because of the chromium metal's containing more gas than the manganese metal and a smaller sample was used. METHOD The measurements were made as follows: The complete system when cold was evacuated and refilled with H2 until all the air was removed. It was then refilled with H2 to the desired pressure, as indicated on manometer B. The temperature was then raised to the desired value and as gas was either liberated from or absorbed by the sample, the height of well H was changed to alter the volume of the system so as to keep the pressure constant. In determining rates of liberation of gas, volume readings were taken at convenient time intervals depending on the rapidity with which the gas was liberated. In determining total volumes, the specimen was held at constant temperature and pressure until

Jan 1, 1948

By Irwin Roman

In studying the possibilities of a continuously recording magnetometer for use along the surface of the earth and in an airplane, the Federal Bureau of Mines was led to a study of the theoretical resolving power of magnetic observations, both in the variation of the total magnetic intensity and in each of the two cornponents ordinarily measured. Along with this general study, an attempt was made to determine the relative worth of the total intensity anomaly and the vertical anomaly in geophysical prospecting. Genera1 considerations led to three conclusions: I. In the northern magnetic hemisphere of the earth, the total intensity anomaly is offset to the south of the vertical anomaly, for a positive anomaly (see Appendix, note 1). 2. The resolving power of magnetic observations decreases rapidly with distance from the disturbing body. 3. The horizontal anomaly has little value in prediction of the disturbing body but might be useful in making a choice between bodies suggested by the vertical or total anomaly. Some of the considerations leading to these conclusions were: I. The normal intensity and the anomalous intensity are vectorially additive; hence for a positive anomaly in the northern magnetic hemisphere the total intensity will be a maximum at some point south of the disturbing body and north of the point at which the line to the disturbing body is parallel to the normal earth's field. The anomaly itself has a maximum value directly above the body. For a positive anomaly of constant magnitude, the total intensity will be a maximum when the anomaly vector is parallel to the normal vector. This is shown schematically in Fig. I (not to scale) for a magnetic distribution not restricted to a relatively thin sheet in the magnetic meridian. The normal field has a magnitude 10 with vertical component V0 and horizontal component Ho. Six station points along a traverse across the body from south to north are shown at M to S. At each of these stations the normal magnetic field vector terminates at F. At each of these stations the magnetic field vector due to the disturbing body B terminates at A. The line through the station point and the point A passes through B. The magnitude of the anomaly, indicated by the length of the vector terminating at A, is proportional to some power of the distance from the station point to the disturbing body. If the disturbing body B is a concentrated point of magnetic material, the anomaly is proportional to the inverse second power of the distance. For a uniform magnetic distribution over a line perpendicular to the observed traverse, the anomaly is proportional to the inverse first power of the distance. For surface distributions, the law of intensity is more complicated. At each field point, the total magnetic intensity T is the vector sum of the

Jan 1, 1949

By J. C. Swartz

Measurements of the effect of precipitation stresses on the solubility of cementite (Fe3C) precipitates in a iron are reported. Solubilities were determined from measurements of the Snoek relaxation due to interstitial carbon after quenching from various equilibrium treatments. Stress-free precipitates were obtained by a spheroidizing treatment of vacuum-melted Fe 0.06 wt pet C. Subsequent equilibration treatments were designed to suppress nucleation of other precipitates. The results for stress-free cementite give a heat of solution of 14.8 i 0.2 keal per mole and an entropy change of 1.1 i 0.2 eu in the temperature range 400" to 715°C. Comparison with previous data indicates that the heat of solution increases about 6 keal per mole as temperature increases from 700" to 1000°C. Data on self-stressed cementite in quench-aged specimens of Fe 0.013 wt pet C indicate 1) an apparent heat of solution of 12.1 i 0.4 keal per mole in the range 280" to 690°C, 2) a strain energy of- 1.1 keal per mole Fe3C accompanying precipitation at 280°C, and 3') a gradual decrease in the strain energy of precipitation with increasing equilibration temperature. In com-parison with 2 and 3 the strain energy calculated for an isotropic model is 1.7 keal per mole Fe3C. The lower values obtained from the experiment indicated substantial stress velaxation by dislocation motion. WHEN a supersaturated solution of carbon in a iron is aged at temperatures in the range 200o to 700oC, the carbon clusters by interstitial diffusion and forms cementite (Fe3C) precipitate particles. Unstressed cementite has a volume per iron atom 9 pet higher than that of a iron;' hence, cementite precipitate particles are usually under pressure from the iron matrix. The pressure would tend to increase the solubility of cementite in iron.' This report describes anelastic measurements of the solubilities of self-stressed and stress-free cementite in a iron. Previous determinations of the cementite solubility are summarized in Table I. The method of cementite formation for each reference was studied to ascertain the state of stress of the cementite. The results judged to be for stress-free and stressed cementite are distinguished in the table. In the next section an estimate of the stress effect is obtained which is clearly too small to account for the large difference between the previous results in parts A and B of the table. THEORETICAL Let AGO be the standard free-energy change of the reaction Fe3C (eem.) = 3Fe (a) + C (in a) [1] in the absence of stresses. Since cementite precipitates appear to be rather pure10 and the carbon is so dilute in the iron,8 the cementite and iron of Eq. [ I] for the stress-free case have essentially unit activities and the activity of carbon equals its atom fraction xoC Then the stress-free equilibrium is expressed by RT In XoC = -?GO 121 To first approximation the change in the chemical potential of carbon due to the precipitation stresses equals the elastic strain energy W accompanying precipitation of a mole of cementite.2 Hence, in the presence of the precipitation stresses the equilibrium is described by RT In x sq = -?G° + W [3] where xsC is the mole fraction of dissolved carbon in the stressed case. An approximate value of W can be obtained from analysis of the inclusion problem in elasticity theory. The inclusion is a small portion of the matrix phase which has suffered a transformation while still imbedded in the matrix. In the absence of the constraint of the matrix the transformation would be equivalent to a uniform dilational strain eT. Both the matrix (a) phase and inclusion (0) phase are assumed to be homogeneous, isotropic materials. When the a and 0 phases have the same elastic moduli, which is approximately true for iron and cementite,11 the total strain energy per mole ß is12 2µVß(eT)2(3 +4 µx)-I [4]

Jan 1, 1968

By J. D. Wood, J. T. Smith

ALLOYS with a dispersed second phase in a metallic matrix are generally much stronger than the matrix itself. Plastic deformation in dispersion-strengthened alloys is usually confined to the matrix phase when recovery processes are active, while in the absence of recovery both phases may yield.' The alloy system studied in the present research was WC-12 wt pct Co and consisted of noncoherent WC particles dispersed in the cobalt matrix. Some particle-to-particle contact existed but not enough to produce a continuous WC skeleton. The microstruc-ture of the WC particles was characterized by very straight edges, forming a trapezoidal shape in any plane of polish. Previous investigations with WC-Co alloys at room temperature have shown that fracture of the WC particles occurs in transverse rupture testing.' Room-temperature slip was reported for WC particles after indentation for hardness measurements.3 Elevated-temperature deformation of WC particles in a WC-12 pct Co alloy was suggested by recent electron microscope studies of specimens deformed at 900' to 1000°C.4 In highly deformed alloys, the WC edges were serrated in contrast to the usual straight or smooth appearance. WC-12 pct Co and WC-15 pct Co alloys have been previously studied under elevated-temperature com-pressive-creep conditions by the present authors. Electron microscope studies of two-stage replicas from deformed specimens showed no evidence of slip or fracture of the WC particles. These specimens were brought to temperature and allowed to equilibrate prior to the application of the creep load. It was believed that the load-application rate, a crosshead speed of 0.005 in. per min on an Instron universal testing machine, was sufficiently low that recovery within the cobalt matrix was sufficient to limit the deformation to this matrix. A series of experiments was performed to evaluate the influence of loading rate on the deformation of WC-Co alloys. A WC-12 pct Co alloy was selected for these determinations. The average WC particle size was 4.45 p with an average linear separation between particles of 0.59 p. The selected temperature was 800°C and was monitored with a Chromel-Alumel thermocouple attached to the specimen. Testing was conducted in an argon-atmosphere chamber to prevent oxidation of the WC-Co specimens. This chamber was mounted on an Instron universal testing machine equipped to apply the load at a fixed rate. Each specimen was loaded to 110,000 psi compression stress at 0.05 and 0.5 in. per min. The loading rate was monitored prior to insertion of the test chamber and was found to be almost precisely the nominal rate selected. The specimens were raised to temperature and held to equilibrate with the surroundings, and then the load was applied and held for 4 hr to duplicate the exposure time utilized for the creep specimens. The time to reach full load at a crosshead speed of 0.005 in. per min was some 500 sec and was reduced to 50 and 5 sec as the loading rate was increased to 0.05 and 0.5 in, per min, respectively. The model developed by Ansell,' when recovery processes do not occur, considers that fracture or deformation of the dispersed particles is necessary to relieve back stresses on dislocation sources and allow dislocations piled up against particles to sweep out in the matrix to cause plastic deformation; he further states that, even at elevated temperatures, the dispersed-particle deformation is necessary for yielding in the absence of recovery. For the case of straight dislocation segments piled up against a straight barrier, such as the straight-sided WC particles, the shear stress, 7 exerted on a particle is: where h is the spacing between particles (0.59 p), a is the applied stress (110,000 psi), p, is the shear modulus of the matrix (6.7 X lo6 psi at 80O°C), and b is the Burgers vector of the matrix dislocation. From Eq. [I], the shear stress, 7, exerted on the WC particles when no recovery occurs is of the order of 6 X lo6 psi at 800°C. The limiting stress, F, that will

Jan 1, 1969

By H. R. Peiffer

Hardening of soft metals can be accomplished by dispersing finely divided hard particles in them. The dispersing of finely divided alumina in silver in the presence of oxygen yields a high strength material which is unusual in that its mechanical properties above the melting point of the continuous Ag-O alloy matrix are similar to other solids. The tensile strength is studied for two of these alloys, one of which contains 15 pct by weight alumina and the other 20 pct by weight alumina. The average fracture strengths above 960°C of these alloys were found to be 0.4 x106 dynes per sq cm and 3.8x106 dynes per sq cm respectively. The strengths appenred to be independent of temperature above 960° C. The creep behavior of the 20 pct alumina material was studied above 960°C. The initial creep rate, 6 , of this material can be represented by where s is the applied stress and E the activation energy for the process. This energy is of the order of 1.7 to 2.1 ev. HARDENING of soft metals by the addition of finely divided, hard particles has resulted in the production of materials with excellent creep resistance and with inhibited recrystallization.' It has been demonstrated that such composites have useful strength up to temperatures very near the melting point of the soft metals, but one might expect that the strengthening by the dispersed particles ceases to be of importance above the melting point of the softer phase. This, however, is not so.2 In this paper the strengthening of a liquid Ag-O solution by the presence of dispersed alumina is discussed and experimental data concerning the mechanical properties of such a material at temperatures above 960°C presented. EXPERIMENTAL PROCEDURE Specimens were prepared using powder metallurgical techniques. Finely divided silver oxide was mixed in the appropriate proportions with "Linde B" alumina. For these experiments the specimens contained 15 or 20 wt pct alumina in pure silver.* These alloys were used in these experiments since they were the ones that could be handled readily enough to yield experimental data. Silver oxide was used in preference to silver because it is readily available in a very finely divided form and because the presence of excess oxygen in the silver is important to the properties2 of the material. The powders were mixed wet, using alcohol as the medium, in an ordinary food blender until a uniform mixture was obtained. They were then dried and heated to reduce the silver oxide to silver. Only a fraction of the finely divided silver remains unoxi-dized upon removal from the oven since the finest particles of silver oxidize immediately upon contact with air. The remaining fine silver served as a binder during pressing. The mixture was then pressed at 20 tons per sq in. into shoulder-grip (reduced section 1/4 in. by l/4 in. by 1 1/4 in.) and rectangular bar specimens (l/4 in. by 1/4 in. by 2 in.). The green specimens were heated very rapidly in a globar furnace to 1000°C, held at temperature untic they had reached theoretical density and then furnace cooled. The strength of the two compositions at temperatures above 960 °C was determined by pulling shoulder grip specimens inside a furnace mounted on a tensile machine. Specimens were gripped by means of wires wrapped around the shoulders of the specimen. Temperatures were measured by means of a chro-mel-alumel thermo-couple placed in the vicinity of the specimen. Control of temperature (within ±°15C) was accomplished by means of a Weston Recorder-Controller. Before loading, specimens were held at temperature for approximately 15 min in order to insure uniform specimen temperature. The low loads were measured by a special load cell designed by Baldwin Lima Hamilton. All testing was performed on a FGT testing machine of the same com-pany. Creep studies were performed in bending utilizing rectangular specimens of the 20 pct alumina alloy. Specimens supported at both ends by knife edges of inconel were placed in a globar furnace, heated quickly to temperature, and the deflection of the beam measured optically as a function of time. The weight and size of the specimen were predetermined and the maximum stress on the beam calculated from

Jan 1, 1962

By M. B. Kasen

eralized strain equation appear quite different they are really identical. This identity can be shown in a simple mathematical rearrangement. Referring to Eq. [I], the substitution of ln(1 +?E) for ? (where ?E is the engineering strain) yields: a =s8- (s8?so)e?1/?c) ln(1 +s8??E) [4] or s =s8?(s8?so)(l +?E)-1 [5] Replacing (1 + cE) with its equivalent, (l/lo): s=s8?(s8?so)l/€c [6] Adding and subtracting the quantity (s8 - so) yields: s=s8?(s8?so)+ (s8-so) l-(^)l/£c [7] = s0+(s8?so)ri-(^0)1/^l [8] Letting n = 1/?c it follows that: This equation will be seen to be identical to the generalized strain expression in Eq. [3], the coefficients a and b being equal to so and (s8?so)/?c or n(s8?so), respectively. Confirmation of the relationship noted above was provided by fitting experimental stress-strain data5 for 304 stainless steel (total strain from 0.072 to 1.15) at room temperature at a true total strain rate of 4 x 10-3 sec-1 to Eqs. [I] and [3]. In this study nonlinear regression analyses were used to evaluate the equation constants. The results of this evaluation are presented in Table I. When these constants are used in Eqs. [I] and [3] the curves obtained are coincident. It will also be noted that the value of n is equal to YE,, the value of a is equal to so, and the value of b is equal to (s8 - so)/Ec. These equalities are illustrated in Table I where the Voce constants in parentheses were calculated from a, b, and n values. Excellent agreement is seen to exist. It is concluded, therefore, that the Voce equation is, indeed, identical to the linear expression involving generalized strain. In applying the generalized strain concept to stress-strain data, it has been noted3 that data within what was termed the transition region (first few points in the plastic flow region) must be excluded from the analysis in order to obtain the linearity in Eq. [3]. A similar exclusion applies in the use of the Voce equation since an expression which would describe the strain-hardening region would usually be found to be not too effective in the elastic-plastic fillet2 which connects the elastic line to the strain-hardening region. These considerations further substantiate that Eqs. [I] and [3] do indeed describe identical behavior. Note added in proof. Since this manuscript was submitted for publication, correspondence with Professor S. R. Davies, University of Edinburgh, (of Ref. 3) indicated that his associates have also confirmed the identity between the Voce equation and the generalized strain concept. It is sometimes desirable to obtain a small grain size in super-purity metals. Unfortunately, the absence of impurities, the low recrystallization temperatures, and the low activation energies for boundary motion result in rapid growth of relatively few grains when conventional recrystallization practices are used. For example, Arajs et al.1 were unable to obtain a mean grain diameter less than about 0.4 mm in iron containing 38 at. ppm of impurity. The <1 at. ppm purity range in many modern superpurity metals results in yet larger limiting grain sizes. It is the purpose of this communication to describe a technique by which mean grain diameters as small as 30 µ have been produced in aluminum having an impurity content < 0.5 at. ppm. The technique should be applicable to superpurity metals other than aluminum and has potential applications to grain refinement of commercial alloys. The necessary and sufficient requirements for production of a small grain size are as follows: a) a large number of potential nucleating sites must be created randomly within the cold worked material, b) sufficient thermal energy must be provided at a rate that will simultaneously activate a large fraction of the potential nuclei, and c) the grain growth must be stopped shortly after grain impingement.&apos; A high density of potential grain nuclei may be cre-

Jan 1, 1970

By R. M. Genevray, M. B. Bever, E. J. Suoninen

THE martensitic transformation in the ß-phase of the Cu-Zn system has been the subject of several investigations. The transformation is known to be reversible and to be affected by stress. Its temperature range has been determined as a function of composition. In the investigation reported here, the effect of tensile stresses on the transformation was investigated quantitatively. Some information was also obtained on the thermoelastic behavior of the martensite formed in the first stages of the transformation. Most of the experiments were done with alloy E of an earlier investigation;&apos; this alloy analyzed 60.49 pct Cu and 39.51 pet Zn by weight. The methods of shaping and heat treatment were also essentially the same as those previously used. The stress was applied to the specimen immersed in a cooling liquid. The transformation was followed by measuring the electrical resistance with a Kelvin bridge and the elongation with a cathetometer. Fig. 1 shows the M, temperature as a function of stress. Resistance and strain measurements gave essentially identical values. The results suggest a roughly linear relation between M. and in the range investigated, up to 12 kg s mm". At higher stresses, plastic deformation begins to interfere seriously with this relationship. The increase of M, with stress is consistent with published work on the effect of stress on the martensitic transformation. The slope of the curve, 4°C per kg mm ", is of the same order of magnitude as the corresponding value calculated for steel.&apos; Fig. 1 also shows the difference, AM, between the temperature of 50 pct transformation on cooling, as measured by changes in length, and that of 50 pct reverse transformation on heating. This difference, which may be considered a measure of the hysteresis, increases with stress; the decrease at highest stresses is probably associated with plastic deformation. Preliminary work using only resistance measurements was done with an alloy containing 60.15 pct Cu and 39.79 pct Zn by weight. The results indicated higher values o-F M, in agreement with the known variation of M. with composition.&apos; The effect of stress on M, (2°C per kg mm-&apos;) was of the same order of magnitude as that shown in Fig. 1 for composition E. An increase in hysteresis with stress was also found. The following experiment was made in order to investigate a partially transformed structure. A specimen of alloy E was cooled to — 85°C under a stress of 4.7 kg mm-&apos;. Under these conditions, the martensitic transformation started but did not go to completion. The stress was then released and the specimen cooled to — 105°C. Fig. 2 shows the measured elongation c. The first change in the slope of the curve indicates the beginning of the transformation under stress. Removing the load at —85°C caused a decrease in length to the value corresponding to the elastic elongation of the parent phase resulting from the applied stress. Hence, the marten-site formed in the first part of the experiment apparently disappears completely and without hysteresis upon the release of the stress. The increase in length on further cooling indicates renewed formation of martensite. These conclusions are consistent with the concept of "thermoelastic" martensite," which has been confirmed by test." Acknowledgments The authors are greatly indebted to Professor M. Cohen for his advice and encouragement. They also thank F. Paxton for assistance. Thanks are due the American Brass Co. which supplied the alloys. References E. Kaminsky and G. V. Kurdjumov: Zhur. Tekhn. Fiziki SSSR (1936) 6, p. 984. A. B. Greninger and V. G. Mooradian: Trans. AIME (1938) 128, p. 337. "J. E. Reynolds, Jr. and M. B. Bever: Trans. AIME (1952) 194, p. 1065; Journal of Metals (October 1952). &apos;A. L. Titchener and M. B. Bever: Trai~s. AIME (1954) 200, p. 303; Journal of Metals (February 1954). " 3. A. Kulin, M. Cohen, and B. L. Averbach: Trans. AIME (1952) 194. p. 661; Journal of Metals (June 1952). "J. K. Pate1 and M. Cohen: Acta Metallurgica (1953) 1, p. 531. &apos;C. Crussard: Comptes Rendus (1953) 237, p. 1709. &apos; G. V. Kurdjumov: Zhur. Tekhn. Fiziki SSSR (1948) 18, p. 999. G. V. Kurdjumov and L. G. Khandros: Dokl Akad. Nouk. SSSR (1949) 66. p. 211.

Jan 1, 1957