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By P. Gordon

An isothermal jacket microcalorimeter, supplemented by metallographic, microhardness, and X-ray measurements has been used to study the isothermal annealing of high purity copper after room temperature tensile deformation. The amount of stored energy released during annealing has been measured as a function of deformation in the range 10.8 to 39.5 pct elongation. The data have shown the major heat effect to be associated with recrystallization and have allowed an analysis of the recrystal-lization kinetics and the calculation of activation energies of recrystallization. WHEN a metal is deformed plastically, some of the energy expended is dissipated as heat during the working process, while the remainder is stored within the metal in the form of lattice distortions and imperfections. During subsequent heating of the metal, the distortions and imperfections can be largely annealed out and the associated stored energy released as heat. It is apparent that measurements of the evolution of stored energy during such annealing may produce important information concerning the nature of the annealing mechanisms and the imperfections involved. Some excellent studies of this type have been made in the past, notably those of Taylor and Quinney,' Suzuki,2 Bever and Ticknor,3 Borelius, Berglund, and Sjöberg,4 and Clarebrough et al.5,6 None of this work, however, employed isothermal techniques, with the exception of the Borelius studies' in which only the early annealing stages were investigated. Since isothermal measurements, as compared with heating or cooling curve, have the merits that 1—they reveal the kinetics of a process more clearly, 2—the results obtained are more easily applied to theory, and 3—most fundamental investigations of annealing using techniques other than calorimetry have been carried out isothermally, it was considered important to apply calorimetry to the study of the isothermal annealing of metals. Accordingly, an isothermal jacket calorimeter of the Borelius type,' supplemented by metallographic, hardness, and X-ray measurements, has been used to study the annealing of high purity copper after room temperature tensile deformation. Experimental The microcalorimeter has been described fully elsewhere." Briefly, the specimen to be studied is placed in a constant temperature environment of virtually infinite heat capacity achieved, as shown in the drawing of Fig. 1, by means of a vapor thermostat. A high thermal resistance is provided between the sample and the environment and a sensitive differential thermopile (see Figs. 2 and 3) arranged with half its junctions in contact with, and thus at the constant temperature of, the environment, and the other half in contact with the sample. A reaction in the sample develops a small difference in temperature, AT, across the thermopile, which is followed by a recorder-galvanometer set-up as a function of time, t, and is converted to reaction heat per unit time, P, by the use of the equation AT P=a?T + b AT dt The constants, a and b, in Eq. 1 are determined by a simple calibration, making use of the Peltier heat developed by a small current run through the junction of a thermocouple located in an axial hole in the specimen (Fig. 2). In its present form, the limit of sensitivity of the calorimeter is a heat flow of 0.003 cal per hr. The copper used was the spectroscopically pure metal supplied by the American Smelting and Refining Co. in the form of 3/8 in. diam continuously cast rod, reported to be 99.999+ pct Cu. A small amount of the copper was available at the start of this work and is referred to hereafter as lot A. A second batch, lot B, was obtained later, most of the results described subsequently being for this lot. As will be seen, there is some indication that lot A was somewhat purer than lot B, but it is not known whether this difference was present in the as-received metal or arose during subsequent handling. The two lots of copper were remelted and cast into two 1½ in. diam ingots in vacuo, using high purity graphite crucibles and molds. The ingots were upset several times to break up the large cast grains, and then rolled and swaged to rods 0.391 in. in diameter, using several intermediate anneals with about 40 pct reduction in area between anneals. The penultimate anneal was 2 hr at 350°C. X-ray examination showed no marked general preferred orientation in the resulting rods. The grain structure typical of the two rods is shown in the micrograph of Fig. 4." It was found to be virtually im- possible to get an unambiguous measure of the absolute grain size in the two annealed rods because of the profusion of annealing twins and the lack of regularity of the grain boundaries. However, counts of the number of boundaries intersected per unit length along a random line on a polished section, making a correction for the proportion of boundaries (about half) estimated to be twin boundaries, gave a figure of about 0.015 mm for the average grain diameter. The grain size of the rod from lot A was about 5 pct smaller than that from lot B. The rods were cut into 1 ft long bars and these deformed in tension at room temperature to various total elongations in the range 10.8 to 39.5 pct. A strain rate of 1 pct per min was used. The deformed bars were then stored in a dry ice chest until such time as samples were to be cut from them. Five bars deformed as indicated in Table I were used for the subsequent tests. In all cases, all the calorimeter.

Jan 1, 1956

By N. S. Stoloff, J. N. Mushovic

Age hardening response of a Mg-Th-Zr alloy has been studied at temperatures in the range 60° to 450°C. Transmission microscopy revealed clustering of thorium atoms at low aging temperatures, supporting a previous report of GP zone formation. Peak strengthening, which is observed at 325°C, is due to the formation of a coherent, ordered, DO19 type superlattice structure, of Hobable composition Mg3Th, as plates parallel to the matrix prism planes. These plates later reveal a Laves phase structure of composition Mg2Th. The equilibrium Mg4Th phase begins to precipitate in two different forms at an early stage, competitively with the Mg2Th plates. RECENT work on the Mg-Th system indicated that, unlike most magnesium-base alloys, complex precipitation phenomena may be occurring. The partial phase diagram of the Mg-Th system indicates that an equilibrium phase, Mg5Th, is the sole intermediate phase.' sturkey,' however, has reported, using X-ray and electron diffraction techniques, that a metastable fcc Laves phase, Mg2Th, precedes the formation of the equilibrium compound, which he identified as closer in composition to Mg4Th. Murakami et al.3 reported that the equilibrium phase precipitates preferentially on grain boundaries and dislocations in a Mg-1.7 wt pct Th alloy; Kent and Kelly4 aged a more dilute alloy, Mg-0.5 wt pct Th, for 4 days at 220°C and found similar results. In addition, they reported that a platelike phase with a structure close to that of the magnesium matrix forms perpendicular to the basal plane and is probably ordered. Research on a Mg-4 wt pct Th alloy by electrical resistance measurements and transmission electron microscopy has suggested that GP zones may form at low aging temperatures.3 However, the electron micrographs purporting to show this phenomenon were not conclusive. In view of the fragmentary evidence concerning the nature of the precipitation processes in the various Mg-Th alloys, an aging study was undertaken to clarify the characteristics of the various precipitates which form and to correlate the mechanical properties of the system with the direct precipitate-dislocation interactions. The latter results are presented elsewhere.' The purpose of this paper is, therefore, to discuss the precipitation sequence in this system. EXPERIMENTAL PROCEDURE Sheet stock (0.060 and 0.010 in. thick) of a commercial Mg-3.93 wt pct Th-0.42 wt pct Zr alloy (designated HK3lA) similar to that studied by sturkey2 was supplied through the courtesy of Dr. S. L. Couling of Dow Metal Products Co. Zirconium does not enter into any precipitation reactions,' but is present primarily as a grain refiner. The alloy was chill cast, warm rolled to 0.090 in. thick stock, and then finally reduced by a combination of hot and cold rolling. The alloy chemistry is given in Table I. This material was solution treated at 580°C for 4 hr in a dry CO2 atmosphere, and then water quenched. Material in this condition was fairly clear of precipitate particles and was fully recrystallized. Aging at temperatures less than 200°C was accomplished by immersing the alloy in a silicone oil bath; for higher temperatures, aging was done in a salt pot. Age hardening treatments were conducted at 60°, 80°, 105°, 135°, 160°, 250°, 325°, 350°, and 450°C for times ranging from 5 min to 400 hr. Hardness tests were performed on chemically polished 0.060-in.-thick blanks of solution treated material which were aged at the various temperatures for increasing lengths of time. For aging temperatures above 150°C the Rockwell Superficial 30T scale was employed, while samples hardened at temperatures below 150°C were monitored with the 45T scale. Each data point consists of at least three separate readings. Yield stresses also were measured at room temperature on both 0.060 and 0.010 in. sheet specimens aged at 325°C. The aged foils were thinned by the window method in a solution of 80 pct absolute alcohol and 20 pct concentrated perchloric acid (70 pct) maintained at 0°C. A stainless steel cathode was used and the applied voltage was 10 to 15 v. Thinned samples were rinsed in distilled water and pure methanol. After the me-thanol rinse the thin foils were quickly dried between filter paper. Foils prepared by the above method were examined in a Hitachi HU11B electron microscope operating at 100 kv. RESULTS A) Hardness. The hardness data are depicted in Figs. 1 and 2. Peak strengthening occurs at 325°C after aging about 6 min, see Fig. 1. Significant strengthening is achieved also at 350°C, but aging at 450°C produces only softening. The stepped curve at 250°C indicates that a complicated precipitation process may be occurring at that temperature. Fig. 2 suggests that at least two hardening mechanisms exist since the lowest temperature hardness peaks are displaced to the left of the peaks obtained at 135° and 105°C. A great deal of scatter is observed at long times in all cases due to magnesium surface degradation caused by the silicone oil bath. B) Identification of the Strengthening Precipitates. The structure formed atlowagingtemperatures (c10O°C) was not clearly resolvable by transmission microscopy. The only bright-field evidence for a change in structure was a mottled appearance which could be observed at extinction contours, as shown in Fig. 3(a), and the disappearance of this effect when dislocations produced under the influence of the electron beam passed through the matrix, as noted in

Jan 1, 1970

By A. H. Larson, R. J. McClincy

Laboratory-scale decopperizing experiments with multiple sulfur addifions were conducted at 330°C on ternary Pb-Cu alloys containing, as the third elenlent, Sn, Ag, As, Sb, Bi, Zn, and Au, common impurities in lead blast-furnace bullion. For silver and tin, an increased rate and extent of 'cofifier removal was obsert3ed. The elements As, Sb, Zn, Au, and Bi had no effect or less effect as compared to sulfur additions with no i)npurily additions. THE production of primary lead in the blast furnace yields an impure lead frequently containing such impurities as copper. antimony. arsenic. tin, gold, silver iron, oxygen. and sulfur. By cooling this lead to a temperature near its melting point. most of the iron, sulfur, and oxygen and part of the other impurities are removed in the form of a dross. With incipient solidification of the lead, the copper concentration wil have been reduced to 0.02 to 0.05 pct. depending upon the concentration of the other impurities. according to Davey.' Since copper interferes with the treatment of silver after the desilverizing process, it is desirable to decrease the copper content of the lead still fur-ther before the lead is desilvered. The decopperizing of the lead is accomplished by stirring a small quantity. approximately 0.1 pct. of elemental sulfur into the lead at a temperature near its melting point, 330" to 360°C. The copper is removed as a copper sulfide which constitutes a small fraction of a voluminous dross consisting mostly of lead sulfide and entrained metallic lead. The residual copper concentration following the decopperizing operation is frequently as low as 0.001 to 0.005 pct. Thi fact has aroused considerable interest because the equilibrium copper concentration of lead in contact with solid PbS and solid Cu2S is at least an order of magnitude greater, 0.05 pct Cu at 330C. 1, 2 Most investigators have suggested that various impurities in the lead bullion are responsible for the very low copper concentrations frequently encountered in practice. There is little agreement, however? as to which of the impurities are helpful and which are not.3"11 Also. few investigators have sought to explain the mechanisms responsible for the removal of copper to very low concentrations. Willis and Blanks9 have proposed that a nonstoichiometric copper-deficient cuprous sulfide forms in place of the supposed Cu2S. Being copper-deficient, this sulfide phase would possess a low copper activity, and the diffusion of copper dissolved in the liquid lead into this phase would be greatly facilitated. Pin and wagner2 have investigated the removal of copper from liquid lead by studying the effect of impurity-doped lead sulfide on the decopperizing of pure Pb-Cu alloys. Samples of the doped PbS were held in contact with copper-saturated lead for 1 week at 33'7°C. They reported a beneficial effect on decopperizing with bismuth and antimony and no effect with tin or silver. which is directly opposite to the results observed in practice and those reported by Davey 3 and this studv. The purpose of this paper is to describe the effects of certain additive elements on the extent to which copper can be removed fro111 liquid lead by successive additions of sulfur. The impurity elements were added individually to prepared Pb-Cu alloys. The resulting ternary alloys as well as a binary Pb-Cu alloy were then decopperized with repeated additions of sulfur. EXPERIMENTAL Materials. Granulated test lead with a purity of 99.999 pct and the additive elements Cu. Ag. Sb. Bi. Zn. Sn. and Au with purities of 99.99 pct were American Smelting and Refining Co. research-grade materials. The major impurities in the lead were 1 ppm each of iron and copper. all others being less than 1 ppm. The arsenic used was a technical-grade arsenic of 98+ pct purity. Reagent-grade flowers of sulfur were melted under argon to provide small pieces free of fines. Apparatus. The decopperizing experiments were carried out in a 25-mm-OD by 375-mm-long Pyrex tube sealed at one end. The tube was mounted vertically in a resistance-heated. hinge-type tube furnace controlled to within ±lcC. Temperature measurement was accomplished by means of a standardized chromel-alumel thermocouple sealed into the base of a silica. paddle-type stirring rod. All decopperizing experiments were carried out under an argon atmosphere. Procedure. A Pb-Cu starting alloy containing 0.05 pet Cu was prepared under carbon and poured into cold tap water to produce shot. The ternary alloys were prepared by melting together 100 g of the starting alloy and a sufficient amount of the impurity element to yield the desired concentration. The resulting alloy was then homogenized in a Pyrex tube at 450C with continuous stirring. The furnace temperature was then lowered to the operating temperature of 330°C. When thermal equilibrium had been obtained at the operating temperature, individual additions of 0.2 pct (0.2 g) of solid sulfur were added to the melt and stirred in. Stirring was continued for a period of 3 min. discontinued for 5 min. and resumed for the remaining 2 min of a 10-min cycle. This cycle was repeated for as many sulfur additions as desired. When the decopperizing experiment had been completed the lead bullion was quenched and samples of the bullion and dross phases were taken for analysis. Results. The results obtained in the decopperizing

Jan 1, 1970

By J. W. Downey, A. E. Dwight, M. H. Mueller, H. Knott, R. A. Conner

Sixty new ternary equiatomic compounds are reported with a hexagonal crystal structure that is isostructural with or very similar to Fe2P, D3h-P62m. HoNiAl is a typical example, with a, = 6.9893 ± 0.0003Å, C, = 3.8204 ± 0.003Å, and c/a = 0.54 7. Three holmium atoms occupy (g): x,0,1/2 three aluminum atoms occupy (f): x,0,0; one nickel atom occupies (b): 0,0,1/2; and two nickel atoms occupy (c): 4, + , 0. The nonequivalent 1(b) and 2(c) sites give rise to two sets of unequal interatornic distances (i.e., Ho-Ni and Al-NL in the case above), which account for the prevalence of Fe2P-type tertmry compounds and the scarcity of binary examples. Unit-cell constants are presented for the sixty compounds and density measurements on the compounds HoNiAl and UFeGa confirm that three formula weights are present per unit cell. Neutron and X-ray powder diffraction intensity measurements were made on CeNiAl and HoNiAl, respectively. The atomic posiLiotml parameters in CeNiAl were determined from neutron data to be x = 0.580 5 0.001 for cerium and 0.219 5 0.001 for aluminum. An investigation of the quasibinary section between the binary compounds CeNi2 and CeA12 revealed a new ternary compound CeNiAl. The compound has a hexagonal structure and is isostructural with the prototype compound Fe2P. Additional examples discovered or confirmed in this investigation provide a total of sixty ternary compounds that are isostructural with or closely related to Fe2P. Previous investigators1'2 reported the unit-cell constants for the hexagonal compounds UFeA1, UCoAl, UIrA1, ZrNiAl, ZrNiGa, HfNiAl, and HfNiGa and the present investigation has confirmed that the compounds are isostructural with Fe2P. Independently, Steeb and petzow3 reported the same structure type for UCoAl, UIrA1, and UNiA1. However, the present results suggest a different atomic site occupancy for the component atoms in the three compounds. A detailed investigation of the relative positions of the three kinds of atoms in the compounds CeNiAl and HoNiAl will be discussed. EXPERIMENTAL PROCEDURE The equiatomic alloys were prepared from elements of 99.9+ pct purity by arc melting under a helium-argon atmosphere. After homogenization at temperatures from 700" to 900' C, a metallographic examination was performed by conventional methods, and density measurements were carried out by the immersion method in CCl4. A powder sample was prepared for diffraction studies by crushing a portion of the annealed button. X-ray diffraction patterns were obtained with a Debye-Scherrer camera, in which the annealed powder was glued to a quartz filament, and indexed with the aid of a Bunn chart. Unit-cell constants were calculated from the computer program of Mueller, Heaton, and Miller4 and d spacings were obtained by the program of Mueller, Meyer, and Simonsen.5 The intensity values were calculated from the relation I, ~ (m)(L.P.)F2 by a computer program written by Busing, Martin, and Levy.6 The absorption and temperature correction factors were neglected. An X-ray study of HoNiAl was carried out to take advantage of: large differences in atomic scattering factors for holmium and aluminum, X-ray patters free of background darkening, negligible oxidation at room temperature, and negligible weight loss in the preparation of this alloy. The neutron diffraction studies were made on a powder sample of CeNiAl contained in a -in. diam V tube and a pattern was obtained with neutrons of wavelength The neutron scattering factors employed (x 10-12 cm). In contrast to the scattering amplitude for X-rays, cesium does not have the largest cross section, however, there is a sufficient difference in the neutron scattering amplitudes to distinguish between the atomic species. The neutron transmission was high, 86 pct; therefore, absorption corrections were not necessary for the cylindrical sample. Most reflections could not be observed individually, because of the relatively large unit cell (a = 6.9756 and c = 4.0206Å) and relatively short neutron wavelength; therefore, the intensity of grouped reflections was considered. The Kennicott modification7 of the Busing-Martin-Levy program6 was employed to determine the identity of the atoms at the various lattice sites and the positional parameters. RESULTS A structure for the prototype compound Fe2P was first reported by Hendricks and Kosting;8 however, the structure was in error. The correct structure, as reported by Rundqvist and Jellinek,9 is as follows. The unit-cell constants and volumes per formula weight (V/M) are given in Table I for the sixty compounds examined in this investigation and classified as Fe2P-type compounds. The structure type was determined initially from a comparison of the unit-cell constants of HoNiAl with other known examples of this structure type1' and from the density of HoNiAl, given in Table 11. The density indicated that three formula weights comprised a unit cell, as in the prototype compound Fe2P. The assignment of the three species to lattice sites was made initially on the basis of atomic size. The large holmium atoms were assigned to the 3(g) sites that have a relatively large interatomic distance to nearest neighbor positions, the small nickel

Jan 1, 1969

By E. T. Turkdogan, L. J. Martonik, R. J. Fruehan

Electrochemical measuretnents of the solid oxide electrolyte galvanic cells CY-Cr2O3 I ZrO2 (CaO) 1 O (in Fe alloy) CY-Cr2O3 I Tho2 (Y2O3)I O en Fe alloy) have been made at 1600°C (2912°F) in order to test the Performance of such cells at liquid steel temperatures. The oxygen pvobe (cell) consists of a disk of ZrO2 (CaO) or Tho2 (Y2O3) electrolyte fused at one end of a silica tube filled with a mixture of Cr-Cr2O3 which is the reference electrode. Upon immersion in liquid steel, the electromotive force readings achieve a steady value within a few seconds, and remain steady for 30 win or more. The perforwzance of the probes has been tested using Fe-O, Fe-Si-O, Fe-Cr-O, Fe-V-O, and Fe-Al-O alloys; the oxygen contents of liquid steel derived from the measured electromotive forces are in satisfactory agreement with those determined by arulysis. Use of the probe in the deoxi-datiorz of steel, in laboratory experiments, is discussed. The results indicate that there is insignificant electronic conductivity in ZrO2(CuO) at oxygen activities down to those corresponding to 10 ppm in steel. At lower oxygen activities, probes tipped with ThOn (Y2O3) disks perform satisfactorily at oxygen activities down to 1 ppm O or less. THE key to the control of deoxidation of steel is a sensing device to measure rapidly the concentration of oxygen in liquid steel in the furnace, ladle or tun-dish at any desired stage of deoxidation. The analysis of the cast steel by the neutron-activation or vacuum-fusion method gives total oxygen as oxide and silicate inclusions. This analysis is important for guidance to steel cleanliness; however, such a postmortem is of little value in the control of deoxidation of liquid steel. At the General Meeting of the American Iron and Steel Institute in New York, 1968, Turkdogan and Fruehan' presented a paper on the preliminary results of the work done in this laboratory on rapid determination of oxygen in steel by an oxygen probe. Details of the work done in this laboratory leading to the development of a galvanic cell for the determination of oxygen in liquid steel, and the results of the tests made are given in this paper. It was through Wagner's contributions, since the early Thirties, to the physical chemistry of semiconductors in general that it ultimately became possible to construct galvanic cells for application at high temperatures. In 1957, Kiukkola and wagner2 successfully demonstrated the use of several solid electrolytes in measuring the free energies of several chemical reactions, in particular, the use of lime-stabilized zir-conia in high-temperature oxidation reactions. Starting 7 years later, a number of papers appeared in the technical literature3-' demonstrating possible applicability of galvanic cells for the determination of oxygen in liquid steel. In the earliest work, Japanese investigators3j4 experimented with various types of reference electrodes, e.g., graphite-saturated liquid iron at 1 atm CO or Ni-NiO mixtures; the results obtained, though promising, were not of sufficient accuracy. Except for the work of Baker and West,6 all other investigators5,7,8 showed that ZrO2(CaO) electrolyte could be used for this purpose. The main part of the galvanic cell used by Fischer and ~ckermann' and by schwerdtfeger7 (the latter work was done in this laboratory), consisted of a ZrO2(CaO) tube, -1 cm ID, closed at one end, with a platinum contact wire fixed mechanically inside the closed end. The tube was flushed with a gas of known oxygen partial pressure, e.g., air, CO-CO2 or H2-CO2 mixtures; gas along with the platinum lead wire served as the reference electrode. The oxygen contents derived from measured electromotive forces agreed reasonably well with the oxygen contents determined by vacuum-fusion analysis. It is evident from recent investigations that the electromotive force technique using a solid oxide electrolyte is fundamentally well suited for the determination of oxygen in liquid steel. However, it is equally clear that the cell arrangement of the type as commonly used is in need of considerable improvement, as it exhibits several shortcomings for industrial and even laboratory use. 1) Because of its size, the zirconia tube, though stabilized, has a poor resistance to thermal shock. 2) Fine pores and microcracks, which are invariably present in zirconia tubes, are detrimental to the satisfactory operation of the cell, particularly when gas reference electrodes are used. 3) Air or carbon dioxide reference electrodes give rise to high electromotive force readings; as a result, the determination of oxygen in steel becomes less accurate. For higher accuracy, the oxygen partial pressure of the reference electrode should be in the range similar to that of oxygen in steel. 4) Even in laboratory experiments, difficulties are experienced when flushing the tube with gases and maintaining the proper gas flow rate. Fischer and Ackermann,' who used air as the reference electrode, reported that when the flow rate was too low, furnace gases would leak into the electrolyte tube, therefore lowering the oxygen potential and measured electromotive force. The required flow rate in order to avoid leakage depended on the tightness of the electrolyte tube which varied with different tubes, thus making it difficult to predict in advance the required flow rate. However, if the flow rate is too high the inside wall of the electrolyte tube would be cooler than the wall

Jan 1, 1970

By S. E. Maddigan, B. R. Zimmerman

Most metallurgists are well acquainted with the contributions already made to the study of metals by the use of X-rays. On the one hand, the radiographic method is constantly becoming of increasing importance as a nondestructive testing procedure, while on the other hand the techniques of X-ray diffraction have made important contributions to the fundamental knowledge in studies of phase diagrams, stress conditions, and so forth. A new, and as yet insufficiently appreciated, tool exists in the application of microradiography to alloy structures. This new procedure in many respects bears the same relation to microscopic investigations as does macroradiography to the gross inspection of metal surfaces. However, where macroradiography is used ordinarily to determine the soundness of the metal structure, this new method can be used not only to investigate micro-un-soundness but also to examine the distribution of the constituent elements within the body of the alloy. When combined with the normal procedures of microscopy, this offers a technique of great potential power. It is intended in this paper to present a few examples of copper-base alloys demonstrating the additional knowledge obtained from the microradiographic method. The detection of micro-unsoundness is demonstrated in Fig. I for a sample of cartridge brass as cast. The sample ap- peared quite sound when viewed under the microscope, but in reality was thickly populated with minute voids. This application of the method conforms in every way to conventional large-scale radiography and has been used to facilitate production of metal for vacuum devices.' The true potentialities of the technique are revealed by comparison of Figs, 2a and 2b, which are respectively a photomicrograph and a microradiograph of a cast alloy of 80 per cent Cu, 10 per cent Sn, 10 per cent Pb. The remarkable difference in appearance provides some concept of the additional information this method may yield when used as an auxiliary to microscopic studies. Fig. 2a shows two phases of the copper-tin system plus segregated_ lumps of lead. Fig. 2b, on the other hand, shows with exceptional clarity the actual dendritic growth of the metal crystals during solidification. The practice of microradiography depends upon the laws of absorption of X-rays. This subject has been reviewed thoroughly in recent papers,l,2,3 but for clarity a brief resume will be given here. As is well known, when a beam of X-rays is transmitted through a, layer of homogeneous material, the intensity is reduced according to the relation: where Il is the transmitted intensity, I0 is the incident intensity, µ1 is the linear absorption coefficient of the material, t1 is the thickness of the material.

Jan 1, 1944

By S. E. Maddigan, B. R. Zimmerman

Most metallurgists are well acquainted with the contributions already made to the study of metals by the use of X-rays. On the one hand, the radiographic method is constantly becoming of increasing importance as a nondestructive testing procedure, while on the other hand the techniques of X-ray diffraction have made important contributions to the fundamental knowledge in studies of phase diagrams, stress conditions, and so forth. A new, and as yet insufficiently appreciated, tool exists in the application of microradiography to alloy structures. This new procedure in many respects bears the same relation to microscopic investigations as does macroradiography to the gross inspection of metal surfaces. However, where macroradiography is used ordinarily to determine the soundness of the metal structure, this new method can be used not only to investigate micro-un-soundness but also to examine the distribution of the constituent elements within the body of the alloy. When combined with the normal procedures of microscopy, this offers a technique of great potential power. It is intended in this paper to present a few examples of copper-base alloys demonstrating the additional knowledge obtained from the microradiographic method. The detection of micro-unsoundness is demonstrated in Fig. I for a sample of cartridge brass as cast. The sample ap- peared quite sound when viewed under the microscope, but in reality was thickly populated with minute voids. This application of the method conforms in every way to conventional large-scale radiography and has been used to facilitate production of metal for vacuum devices.' The true potentialities of the technique are revealed by comparison of Figs, 2a and 2b, which are respectively a photomicrograph and a microradiograph of a cast alloy of 80 per cent Cu, 10 per cent Sn, 10 per cent Pb. The remarkable difference in appearance provides some concept of the additional information this method may yield when used as an auxiliary to microscopic studies. Fig. 2a shows two phases of the copper-tin system plus segregated_ lumps of lead. Fig. 2b, on the other hand, shows with exceptional clarity the actual dendritic growth of the metal crystals during solidification. The practice of microradiography depends upon the laws of absorption of X-rays. This subject has been reviewed thoroughly in recent papers,l,2,3 but for clarity a brief resume will be given here. As is well known, when a beam of X-rays is transmitted through a, layer of homogeneous material, the intensity is reduced according to the relation: where Il is the transmitted intensity, I0 is the incident intensity, µ1 is the linear absorption coefficient of the material, t1 is the thickness of the material.

Jan 1, 1944

By Frances Jane Cromwell, D. J. McAdam, G. W. Geil

In a series of papers, the authors and their associates have shown that the technical cohesion limit is affected by the same four factors that affect the flow stress, namely, the stress system, plastic deformation, temperature, and the strain rate.16-28 Moreover, each of these factors affects the technical cohesion limit in the same way that it affects the flow stress,t The influence of any one of these factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. As the term ilfracture stress' has come into use with the same significance as 'ctechnical cohesion limit," the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. This paper presents the results of an investigation of the flow of notched and unnotched specimens betqrcen yield and fracture, A study has thus been made of the flow and fracture of metals as affected by the stress system, and of the ductility of metals as affected by the stress system throughout plastic deformation. Since two of the principal stresses were equal (S2 = S3), the stress systems can be represented in terms of the radial stress ratio, the ratio of the transverse radial stress s3 to the longitudinal stress S1.* The results of the experiments are represented by a series of their flow-stress curves for each Of the metals investigated, and these diagrams have been used for the development Of Other diagrams Of various types. Ludwik was the first to suggest that fracture occurs when the flow stress becomes equal to a technical cohesion limit. Although Ludwik was incorrect in his view that the technical cohesion limit depends only on the amount of plastic deformation and not On the stress system, he was 'Orrect in his view that the flow-stress curve for any stress system terminates at a point representing a technical cohesion limit. The authors have seen some recent references to assertions by other investigators that a point representing the fracture stress need not be on the flow-stress curve. The Ludwik principle, however, "auld Seem to be axiomatic, provided that the flow Stress and fracture stress are properly defined and that the fracture stress is properly determined. Disregard Of this principle has led to some untenable theories Of criteria for fracture. When a metal is very ductile, the conventional method of determining the ductility and fracture stress by dividing the breaking load by the sectional area after fracture, generally gives values that are much too high. With some metals and in some conditions, the fracture stress thus determined may be two or more times the

Jan 1, 1949

By Robert B. Sosman

THE chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily smaller. I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting on a paper that I had recently published27 on "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of Professor Howe's interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. SCOPE OF THE LECTURE During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyrometric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the United States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the "temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that "temperature of the furnace" is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1948

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium' oxide to form

Jan 1, 1948

By H. H. Keller, E. J. Couch

Damage to production wells subjected to the high temperatures associated with in-situ combustion projects has been a problem since the advent of this thermal recovery technique. Injection of water down the annulus of hot wells has been successfully utilized for cooling and prolonging the life of such wells. A mathematical model that is suitable for predicting the effectiveness of cooling water in a particular application is developed. Typical results for practical ranges of the various parameters involved are presented. INTRODUCTION In the normal course of in-situ combustion operations, highly damaging conditions develop in the production wells as the combustion zone approaches, and these wells are subjected to high temperatures (up to 1500F). The resulting well damage is recognized as one of the more serious operating problems unique to the in-situ combustion process. Even in operations where well completions have been specifically designed to cope with this problem, the question arises as to how this destructively high temperature can be kept within tolerable limits. A simple and economical approach to this problem is to circulate cooling water down-hole. This method has been used with some success in shallow reservoirs. At greater depths, however, the heat exchange with the overburden surrounding the well and between the fluids in the tubing and the annulus tends to equalize the temperatures of the two fluid streams so that the cooling capacity delivered to the bottom of the hole decreases with well depth. This method would provide no appreciable control over the bottom-hole temperature at great depths. In order to delimit the condition under which cooling by water circulation is effective, the wellbore temperature must be related to the water inlet rate and temperature; to the reservoir depth, production rate, and initial temperature; and to the combustion at at bot tom-hole depth. A model that meets these requirements and that will offer an approach for developing engineering solutions to practical design and operating problems is described in this paper. MATHEMATICAL MODEL Previous studies of temperature distributions include those for flowing wells1p2 and those for hot fluid injection. Adams and Haddenhorst 6 presented solutions for the down-hole circulation of hot oil in the treatment of paraffin-deposition problems. In this paper the thermal model presented by Ramey 4 is adapted to the flow system shown schematically in Fig. 1. Water at temperature Ti is injected at a rate wi and flows down the annulus outside the tubing. It mixes at bottom-hole depth D with the fluids produced at race w from the hot reservoir at temperature T. This mlxtureJ. of injected water and reservoir fluids flows up the tubing and is produced at the surface at TI,. In order to describe the temperature response in this system, we make use of the usual conservation of

Jan 1, 1969

By G. K. Manning, A. R. Elsea, A. B. Westerman

A considerable number of high-tem-perature alloys, that is, alloys which have load-carrying ability at elevated temperatures, have been developed on an empirical basis. In order to determine why these alloys possess this particular ability, a project was started at Battelle Memorial Institute on the fundamental factors promoting high-temperature strength of alloys. .4t the time of inception of this study, the cobalt-base alloy, Vitallium, was widely used because of its good high-temperature properties. One phase of this study was to include an investigation of the structures observed in vitalliurn after various heat treatments. Howcver, before investigating the structural features of Vitallium, it appeared logical to examine the phase diagrams of the related binary systems in order to develop information as to which phases might be present in Vitallium. A preliminary survey of the pertinent alloy systems was made, with particular emphasis on the cobalt-chro-mium system, which is the base for the Vitallium series of alloys. The early work of Lewkonja and Guertler2 indicated that cobalt and chro-mium are completely miscible in the liquid state, and, within a narrow temperature range, in the solid state; that the liquidus shows a minimum; and that the alloys containing 45 to 85 pct chromium undergo a transformation at [zoo to 12 50 c More recently, Wever and Haschimoto,3 Wever andLange,4and Matsunaga5 carried Out experimental work which led to the diagrams shown in Fig I and 2. Both diagrams are based on thermal analysis, metallogra~hic, magnetic, and dilatation data; in addition, X ray diffraction results were used by Wever and Haschimoto, and electrical resistance measurements by Mat-SUnaRa. It is apparent from a comparison of the two diagrams that there was a difference of opinion as to the locations of the boundaries of the various phases, and as to the existence of a phase containing approximately 47 pct chromium. With these excep-tions noted, it might be pointed out that the two diagrams are similar, and that, in general, any particular reaction which is shown on both diagrams occurs at a lower temperature on the Matsunaga diagram than on that of Wever-Haschimoto-Lange. Thus, in view of the gaps in the data arid the questionable features in the published diagrams, it appeared desirable to start the fundamental study of Vitalhum by deter-mining the diagram for the cobalt-chro-mi~m system- Experimental Work For the convenience Of the reader, the diagram as determined by the present investigation is presented in Fig 3. The liquidus and solidus data for the low-chromium alloys were taken from the work of Wever and Haschimoto,3 while the melting point for pure chromium is the

Jan 1, 1949

By Arthur F. Taggart

ENGINEERING education today is like a crazy quilt of somber wools and gaudy shoddy, chain-stitched on an academic assembly line, and sold at ever mounting prices to inexperienced youths for lifetime use. Each engineering school offers a half-dozen or so patterns with essentially the same skimpy wool content. Sales appeal is in the color of the shoddy, denoted by the hopeful adjectives chemical, civil and the like. This article is argument for an all wool product made by slow, careful handwork. Bluntly it proposes a thorough four-year undergraduate drill in fundamental science and general engineering empirics, leavened by continuing study of the third of the engineer's troubles: Man. It is not contended that existing methods of engineering education have failed to start men on the path to successful engineering practice (too many of you have started that way); rather, social conditions and the bounds of knowledge have changed tremendously, and corresponding alterations in the pattern of engineering education are overdue. We'll Teach the Specifics The first part of this contention is illustrated by excerpts from a letter received recently from an officer of one of the largest corporations: "We are interested in employing two or three outstanding young engineers to be placed on a special training program to develop them as design and construction engineers.... "We propose to put these men on a four-month indoctrination and orientation course after which they would be given job-training assignments for a period that will vary from about six months to about a year and a half depending upon the aptitudes, abilities and intelligence of the candidates.... "I am not too fussy about what kind of engineers the men might be insofar as academic courses are concerned. They could be.. . in almost any engineering classification.... We can furnish the additional training beyond the academic fundamentals. "The starting rate for these jobs would be $326 per month...." This letter is not unique; rather it is representative of a practice that has become common. It is industry's enforced response to the general refusal by young graduates to submit to union domination in order to gain operating experience at the labor level. The message to engineering schoolteachers is plain: You teach the fundamentals; we'll teach our practice and pay the graduate to learn it. The letter means to the student that time spent in school studying the specific practices of particular industries is waste compounded. The school can't give the equivalent of what industry teaches, wherefore industry will still demand apprenticeship. The student must pay for the specific instruction at school instead of being paid to take it later. And time-consuming specifics crowd out drill in basic scientific and technical subjects as well as liberal arts.

Jan 1, 1952

By Robert B. Sosman

The chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily I I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting On a paper that I had recently published27 On "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of of Howe's interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. Scope of the Lecture During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyro-metric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the united States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the ((temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that " temperature of the furnace " is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1949

By Robert B. Sosman

The chance that a Howe Memorial Lecturer will be able to refer back to a personal contact with the distinguished metallurgist for whom this lectureship is named grows steadily I I did not have the pleasure of his personal acquaintance, but I did receive from him in 1916, quite unexpectedly, a letter commenting On a paper that I had recently published27 On "Types of Prismatic Structure in Igneous Rocks." The paper was written for geologists and petrologists, but it had an application, naturally, to the crystallization of iron and steel in a mold. The letter impressed me at the time, and still does, with the breadth of of Howe's interests and his perseverance in keeping up with the progress of any branch of knowledge that had metallurgical connotations. Scope of the Lecture During several years preceding the date mentioned I had worked in collaboration with Arthur L. Day and E. T. Allen8 at the Geophysical Laboratory, Carnegie Institution of Washington, on the temperature scale as defined by the nitrogen thermometer at high temperatures. Later (1928-1947) I had the opportunity of helping to apply this experience to the pyro-metric problems of the steel industry. Because of the range of its temperatures, the multiplicity of the methods used, and the variety of its purposes, pyrometry in the open-hearth process has always offered a fertile field for both research and development. I am therefore devoting an hour to the subject of temperatures in the basic open-hearth furnace, the furnace that makes most of our steel in the united States. I would direct your attention particularly to the choice of the first two words in the title of the Lecture. One sometimes hears or reads of the ((temperature of such-and-such a furnace," as if it were a single, measurable, characteristic quantity. I need hardly emphasize to any one who has ever operated a furnace or a kiln that " temperature of the furnace " is a meaningless phrase. Even if we confine our attention to the space enclosed by the roof, walls, and hearth of an open-hearth furnace, it is doubtful whether any such space has ever been so uniform in temperature that the phrase would have a meaning. In any furnace, there are many different temperatures, capable of being measured at many different places, and actually being measured for several different purposes. These pyrometric purposes, methods, and results, if given in detail, would expand this lecture into a book on the basic open-hearth process. I must therefore confine myself to a statement of the range of temperatures as they have been observed in various parts of the furnace, indicating in a general way why they are measured, and mentioning the methods that are available without attempting to describe these

Jan 1, 1949

By G. Carman Ridland

In conjunction with a geological investigation of the silver-bearing veins at Contact Lake, Northwest Territories, Canada, a survey was made with a Geiger-Miiller counter of the gamma-ray emissions from the rocks in the vicinity of the mine workings. Discontinuous pitchblende veins have been encountered occasionally in the silver-bearing fissures, and the geophysical survey was undertaken with the hope that abnormally high gamma-ray intensities, if detected, might lead to larger and more continuous pitchblende discoveries. Before the instrument was used at Contact Lake, preliminary tests were made, first with laboratory specimens at Princeton University, and later over known pitchblende deposits at the Eldorado property, LaBine Point, N.W.T. The Geiger-Müller counter, as adapted for field use, is described; the technique of transporting and operating the instrument is outlined; and the general precautions to be observed are discussed. The results obtained at Great Bear Lake show that the instrument is capable of detecting not only a pitchblende ore shoot in a shear zone, but also the mildly radioactive "host rock" at a considerable distance from the ore body. Hence, use of the Geiger-Müller counter is urged, not just for the detailed search for an ore body in a shear zone, but for the detection of possible radioactive "host rocks" in large-scale reconnaissance surveys of unexplored regions made by prospectors and members of federal geological survey parties. Location.—Along the rocky eastern shores of Great Bear Lake, in the Northwest Territories of Canada, lies one of the world's great radium-producing areas. The Eldorado mine, owned and operated by the Eldorado Gold Mines, Ltd., is at LaBine Point; while the Contact Lake mine, operated by Bear Exploration and Radium, Ltd. (B.E.A.R.), lies 9 miles to the southeast of LaBine Point and 2 miles south of Echo Bay, an indentation in the eastern shore line of Great Bear Lake. Geology.—The Eldorado company obtains its radium by the mining of the mineral pitchblende, which is found associated with a complex variety of metallic and nonmetallic minerals1 in quartz-carbonate veins occurring in metamorphosed pre-Cambrian sediment aries. Most of the pitchblende is intimately associated with a brown quartz and belongs to an early hydrothermal stage of mineralization during which safflorite-rammelsbergite and minor cobalt-nickel minerals were also deposited. Some pitchblende occurs with a group of minerals belonging to a later stage of mineralization in which the gangue is mainly dolomite and sometimes ferruginous rhodochrosite. Associated with this group are native silver and lead-zinc-copper sulphide minerals. The Contact Lake property owes its existence to the mining of rich, native silver ore shoots, which are

Jan 1, 1946

By G. Carman Ridland

In conjunction with a geological investigation of the silver-bearing veins at Contact Lake, Northwest Territories, Canada, a survey was made with a Geiger-Miiller counter of the gamma-ray emissions from the rocks in the vicinity of the mine workings. Discontinuous pitchblende veins have been encountered occasionally in the silver-bearing fissures, and the geophysical survey was undertaken with the hope that abnormally high gamma-ray intensities, if detected, might lead to larger and more continuous pitchblende discoveries. Before the instrument was used at Contact Lake, preliminary tests were made, first with laboratory specimens at Princeton University, and later over known pitchblende deposits at the Eldorado property, LaBine Point, N.W.T. The Geiger-Müller counter, as adapted for field use, is described; the technique of transporting and operating the instrument is outlined; and the general precautions to be observed are discussed. The results obtained at Great Bear Lake show that the instrument is capable of detecting not only a pitchblende ore shoot in a shear zone, but also the mildly radioactive "host rock" at a considerable distance from the ore body. Hence, use of the Geiger-Müller counter is urged, not just for the detailed search for an ore body in a shear zone, but for the detection of possible radioactive "host rocks" in large-scale reconnaissance surveys of unexplored regions made by prospectors and members of federal geological survey parties. Location.—Along the rocky eastern shores of Great Bear Lake, in the Northwest Territories of Canada, lies one of the world's great radium-producing areas. The Eldorado mine, owned and operated by the Eldorado Gold Mines, Ltd., is at LaBine Point; while the Contact Lake mine, operated by Bear Exploration and Radium, Ltd. (B.E.A.R.), lies 9 miles to the southeast of LaBine Point and 2 miles south of Echo Bay, an indentation in the eastern shore line of Great Bear Lake. Geology.—The Eldorado company obtains its radium by the mining of the mineral pitchblende, which is found associated with a complex variety of metallic and nonmetallic minerals1 in quartz-carbonate veins occurring in metamorphosed pre-Cambrian sediment aries. Most of the pitchblende is intimately associated with a brown quartz and belongs to an early hydrothermal stage of mineralization during which safflorite-rammelsbergite and minor cobalt-nickel minerals were also deposited. Some pitchblende occurs with a group of minerals belonging to a later stage of mineralization in which the gangue is mainly dolomite and sometimes ferruginous rhodochrosite. Associated with this group are native silver and lead-zinc-copper sulphide minerals. The Contact Lake property owes its existence to the mining of rich, native silver ore shoots, which are

Jan 1, 1946

By A. A. Smith, J. S. Smart

THE controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modem copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range 0 to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously.1-2-3 Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,1, 2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of 3/8-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 850°C. from a surface scale. Test wires were drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at o.3125, 0.257, o.204 and o.162 in., and a final cold reduction of 95 per cent t0 0.081 in. Oxygen-bearing slugs made by remelting were hot-rolled to 5/16 in., drawn to 0.162 in., annealed for 30 min. at 600°C. and cold-drawn 95 per cent to 0.081inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 5/16-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700° to 800°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals were of one hour duration followed by a rapid quench in 10 per cent H2SO4. EFFECT OF PHOSPHORUS The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1945

By C. A. Heiland, Tripp R. M., Dart Wantland

This paper serves to illustrate the application of geophysics to a virtually abandoned mine properly, an application that led to the discovery of an ore body and thus afforded an Opportunity to cOmpare subsequent geologic findings with geophysical data. The work herein described represents, however: more than mere ''case history." It demonstrates that it is possible to obtain satisfactory results by simple means and relatively inexpericnced personnel. The geophysical surveys were made by students as a part of their field assignments in the course of their regular training, and were supervised by Dart Wantland, J. E. Hawkins and R. Maurice 'Tripp. In the course of several seasons an appreciable amount of material was accumulated, which gave graduate students an opportunity for special studies. In this connection, the contributions by L. Massé, R. C. Hyslop, and J. E. Hawkins deserve special mention. The property owners cooperated wholeheartedly in the work, and special thanks are due messrs. J. F. Johnson and S. E. Zelenkov, of the American Smelting and Refining Co., for their interest and for permission to utilize the results of their development work for this publication. Location and Geology The Malachite mine is situated on the northcrn slope of Bear Creek Canyon, 4 miles northeast of Evergreen, I½ miles northwest of Idledale, and 4% miles west northwest of Morrison, in Jefferson County, Colorado. The location (Fig. I) is north of the center of set. 30, T. 45, R. 70 W., at an elevation of about 7500 ft, above sea level, Near the mine the terrain slopes rather uniformly southward at an angle of about 180 pigs. 3 and 7). The geology of the Malachite mine area has been described by J, underhill,' W, Lindgren,2 and J. Boyd.3,4 A map showing surface outcrops and mine workings appears in Fig, 2. the Malachite mine is in an amphibolite belt enclosed in gneisses and schists of the Idaho-Springs formation (probably early Algonkian age). The highly contorted beds are nearly vertical and strike slightly north of west. A series of granite-pegmatite dikes have been intruded almost at right angles into the gneisses and schists and doubtedless are postmineral. While most of the formations are exposed at the surface, a part of the 'lope is covered by slide rock and float, and in the eastern portion by alluvium and creek fill. A quartz-diorite dike cuts through the amphibolite schists at a small angle with nearly vertical dip. The copper sulphides, developed in this dike by magmatic segregation, occur in lenticular form. As far as the mine workings have revealed, the ore lenses are often discontinuous in depth and

Jan 1, 1946

By Tripp R. M., C. A. Heiland, Dart Wantland

This paper serves to illustrate the application of geophysics to a virtually abandoned mine properly, an application that led to the discovery of an ore body and thus afforded an Opportunity to cOmpare subsequent geologic findings with geophysical data. The work herein described represents, however: more than mere ''case history." It demonstrates that it is possible to obtain satisfactory results by simple means and relatively inexpericnced personnel. The geophysical surveys were made by students as a part of their field assignments in the course of their regular training, and were supervised by Dart Wantland, J. E. Hawkins and R. Maurice 'Tripp. In the course of several seasons an appreciable amount of material was accumulated, which gave graduate students an opportunity for special studies. In this connection, the contributions by L. Massé, R. C. Hyslop, and J. E. Hawkins deserve special mention. The property owners cooperated wholeheartedly in the work, and special thanks are due messrs. J. F. Johnson and S. E. Zelenkov, of the American Smelting and Refining Co., for their interest and for permission to utilize the results of their development work for this publication. Location and Geology The Malachite mine is situated on the northcrn slope of Bear Creek Canyon, 4 miles northeast of Evergreen, I½ miles northwest of Idledale, and 4% miles west northwest of Morrison, in Jefferson County, Colorado. The location (Fig. I) is north of the center of set. 30, T. 45, R. 70 W., at an elevation of about 7500 ft, above sea level, Near the mine the terrain slopes rather uniformly southward at an angle of about 180 pigs. 3 and 7). The geology of the Malachite mine area has been described by J, underhill,' W, Lindgren,2 and J. Boyd.3,4 A map showing surface outcrops and mine workings appears in Fig, 2. the Malachite mine is in an amphibolite belt enclosed in gneisses and schists of the Idaho-Springs formation (probably early Algonkian age). The highly contorted beds are nearly vertical and strike slightly north of west. A series of granite-pegmatite dikes have been intruded almost at right angles into the gneisses and schists and doubtedless are postmineral. While most of the formations are exposed at the surface, a part of the 'lope is covered by slide rock and float, and in the eastern portion by alluvium and creek fill. A quartz-diorite dike cuts through the amphibolite schists at a small angle with nearly vertical dip. The copper sulphides, developed in this dike by magmatic segregation, occur in lenticular form. As far as the mine workings have revealed, the ore lenses are often discontinuous in depth and

Jan 1, 1946