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By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members who registered at Institute headquarters during September: William B. Phillips, Austin, Texas. Will L. Clark, Jerome, Ariz. Olof Wenstrom, Boston, Mass. Robert H. Richards, Boston, Mass. Anthony F. Lucas, Washington, D. C. Hennen Jennings, Washington, D. C. P. H. Griffin, New York, N. Y. Waldemar Lindgren, Boston, Mass. H. N. Lawrie, Portland, Ore. C. Snelling Robinson, Youngstown, 0. Clarence P. Linville, Everett, Pa. E. P. Ross, Johnson, Tenn. Members of the XII International Geological Congress who made the Institute Office their headquarters while in New York A. Bigot, Caen, France. E. Gentil, Paris, France. J. Caillebotte, Paris, France. H. Saint-Clivier, Paris, France. John Ashworth, Manchester, England. Tadasu Hiki, Kioto, Japan. T. Dahlblom, Falun, Sweden. L. Milch, Greifswald, Germany.

Jan 10, 1913

By G. Derge, W. Peifer, J. H. Richards

INTRODUCTION A WIDE variety of metallurgical defects in steel have commonly been attributed to the presence of excessive amounts of hydrogen. These defects include flakes in rails and forgings, cracks in welds, and blisters in enameled ware. They have been related to hydrogen largely by circumstantial evidence because the proper sampling and analysis of steel for hydrogen has been known to be difficult and because no general agreement has existed with regard to the relative suitability and accuracy of available methods. The need for a direct approach to these problems has been widely recognized. This general situation has been well described in the publications of the British Committee on the Heterogeneity of Steel Ingots,1 and current approaches to the problem were reviewed in a recent symposium of the AIME.12 The plans described by the present authors at that meeting have now matured satisfactorily and will form the basis of this paper. The principle object of this paper will be to describe the methods of sampling and analysis which have been developed and to illustrate the usefulness and limitations of these methods by citing their application to a specific problem. The first problem selected for investigation was the behavior of hydrogen in rail steel. This was chosen because the occurrence of shatter cracks in rails has received a great deal of study over a long period of time. The defect can be controlled by the expensive procedure of slow cooling. However, it may be hoped that a better understanding of the factors influencing the hydrogen content of rails will lead to a more efficient control of this problem. Rails provide a good starting point for a more general study of hydrogen in steel because they provide a cross section large enough to develop cracks, yet small enough for convenient handling and sampling. Rails were also selected because they are made from plain carbon steel and it was felt that the initial work should not be complicated by the effects introduced by alloying elements. The considerations which determined the original planning of this study should be reviewed. The inherently complex nature of most hydrogen problems requires that a large amount of data must be collected for any particular case. This in turn means that any analytical procedure should be as rapid and simple as possible. The same objective of speed is indicated by the fact that it may finally become desirable to use hydrogen analysis in process control. It is also known that hydrogen is highly fugitive and that any procedure which facilitates early analysis of the sample without prolonged or irregular storage has distinct advantages. The most important previously reported methods of analysis may be classified into three general groups: (I) Vacuum fusion. (2) Vacuum extraction (without melting). (3) Total combustion.

Jan 1, 1948

By W. H. Bassett

W H. BASSETT was elected first vice-president at . the executive session of the new Board on Tues- day afternoon. Karl Eilers, H. Foster Bain, Thomas T. Read, and H. A. Maloney were respectively re-elected as treasurer, secretary, assistant secretary and assistant treasurer. The new Executive Committee will consist of W. H. Bassett, Chairman, and Richard Peters, Jr., H. C. Bellinger, E. De Golyer, Edgar Rickard. The Finance Committee will be J. V. W. Reynders, Chair- man, Henry Krumb and H. G. Moulton. George D. Barron was reappointed Chairman of the Admissions Committee, and F. Julius Fohs put in charge of the Papers and Publications Committee.

Jan 1, 1929

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of the gaseous, topo-chemical reduction of porous hematite spheres. Gas-solid reduction is permitted at each of three advancing interfaces and is controlled by a complex series-parallel sequence of chemical and transport steps. Despite the fact that transport resistances are significant to the advance of each interface, little deviation from linear advance is predicted for the first 98 pct of reduction. Calculations to predict the movement of magnetite /wustite interface by a solid-state diffusion mechanism have been incorporated into the earlier dense-pellet model.' The porous-pellet model is found to give a better description than the dense-pellet one for McKewan's measurements2 of interface movements in dense polycrystalline hematite reduced in hydrogen-water vapor mixtures. THIS paper reports a continuation of work"3" directed toward the better understanding of gas-solid reactions and the development of mathematical models that may be helpful in the design or control of ore-reduction processes. Laboratory studies of the reduction of single oxide samples in tube furnaces normally employ an abundant excess of pure reducing gas. Reduction may appear to be adequately described by a model assuming gas-solid reaction solely at the iron/wustite interface.''' However, when iron ore is reduced in either a fixed bed or an efficiently operated counter-current column, there are portions of the bed where the partially spent gas is no longer capable of reducing wustite to iron. Nevertheless, the formation of the intermediate reaction products, wustite or magnetite, can and does continue. In order to account for this aspect of the reduction of beds of particles, three semiempirical mathematical models were devised.' One of these was for the limiting case of completely dense particles, and two alternatives were provided for porous particles. For purposes of the analysis, a dense pellet was defined as one in which the wustite and magnetite layers were impervious to the reducing gas when the atmosphere was capable of forming iron. In a porous pellet, the intermediate product layers were assumed to be sufficiently permeable to allow reducing gas to penetrate beyond the iron/wustite interface to form wustite and magnetite by removal of oxygen as a gaseous product rather than by a solid-state redfiction mechanism. Further progress required a better understanding of the reaction of the individual particles with the gas stream. A comprehensive mathematical treatment was developed' to describe the continually changing interplay of transport and reaction steps

Jan 1, 1967

By F. Weinberg

Lead single crystals have been deformed in tension over the temperature range of 4.2°K to the melting point. Changes in flow stress resulting from temperature cycling and strain rate cycling have been measured as a function of temperature for crystals of different orientations and purity. It was found that the flow stress ratio, after correcting for the temperature dependence of the shear modulus, decreased progressively with temperature above approximately 0.5Tm. The activation energy calculated from the high-temperature portion of the curve was found to be markedly higher than that of self-diffusion. For single glide crystals, the corrected flow stress showed an increase above 0.5 Tm before decreasitzg with temperature. This increase is attributed to static recovery occurrittg during temperature cycling. THE temperature dependence of the flow stress, based on temperature cycling and strain rate cycling, has been extensively investigated,' and on the basis of these results dislocation models of the work-hardening process have been proposed. In general, the flow stress is divided into two parts, ts, the short-range interaction term, which is only effective at low temperatures and which decreases with increasing temperature, and TG, the long-range stress term, which is independent of temperature after allowing for the temperature dependence of the shear modulus. The observations demonstrating that tG/µ is independent of temperature were generally carried out at low temperatures to minimize recovery effects. Several investigations have been reported on flow stress measurements at high temperatures2"5 which demonstrate that TG/µ does not remain constant at temperatures above 0.5Tm (where Tm is the melting temperature of the material in OK). Specifically, Hirsch and warrington3 carried out temperature cycling tests at two strain rates on single and polycrystalline aluminum up to 0.8 Tm and on polycrystalline copper. For aluminum they found that the flow stress ratio (the flow stress at temperature T2, divided by the flow stress at the reference temperature T1 in one temperature cycle) dropped progressively with increasing temperature above 0.5Tm. From the slopes of the high-temperature portions of the curves, they determined an activation energy for the deformation process of 1.6 ev (at best) which they considered was in agreement with the activation energy of self-diffusion, 1.35 ev. Calculations of the activation volume demonstrated that the deformation was not controlled by dislocation climb. They proposed a mechanism in which the rate-controlling process at high temperatures was due to the rate of move- ment of vacancies away from jogs, i.e., that of self-diffusion. Results of Lucke and Buhler4 on single crystals of aluminum confirmed this conclusion. They measured the critical resolved shear stress of aluminum over a wide range of temperature and strain rates. They found that the temperature dependence of the critical resolved shear stress was similar to that of the flow stress ratio, as determined by Hirsch and Warrington, and from their data calculated an activation energy for high-temperature deformation of 1.35 ev identical to that of self-diffusion. More recently Gallagher5 has carried out a detailed investigation of the temperature dependence of the flow stress ratio of copper, silver, and gold. In all cases, he found that the flow stress ratio, after adjusting for the shear modulus temperature change, drops at high temperatures. The activation energies he determined were found to be appreciably higher than the activation energy of self-diffusion of the material being considered. The flow stress ratio was found to be dependent on the orientation of the material, and, in addition, an anomalous increase in the flow stress ratio for copper, oriented for single glide, was observed above 0.5Tm. The purpose of the present investigation was to measure the critical resolved shear stress, the flow stress ratio, and the strain rate sensitivity of lead, primarily as a function of temperature. The results should indicate whether, following Lucke and Buhler, the critical resolved shear stress of lead has the same temperature dependence as the flow stress, and, following Hirsch and Warrington, whether the activation energy for high-temperature deformation in lead is the same as that of self-diffusion. Lead deforms as a normal fee material,6'7 is available in high-purity form, can readily be grown as single crystals, and, for this investigation, has the very considerable advantage of having a low melting point, 327°C. The observations of the critical resolved shear stress of lead have been published elsewhere.' EXPERIMENTAL PROCEDURE The experimental procedure was essentially the same as that used in the critical resolved shear stress measurements.' Single crystals of 99.999 pct (59) and 99.9999 pct (69) lead were deformed in tension with a table-model Instron in a silicone oil bath above room temperatures and in a cooled methyl alcohol or liquid-nitrogen bath below room temperatures. The test specimens were rectangular in section, 0.65 by 0.33 cm, and had a 5-cm gage length. The specimens were grown as single crystals with tapered ends, which fitted into matched tapered grips for testing. To obtain the flow stress between two temperatures, specimens were first deformed approximately 1.0 pct at the higher temperature. The test was then stopped, the load relaxed, the oil bath removed without disturbing the specimen, the grips and specimen cooled with a fan and then immersed in liquid nitro-

Jan 1, 1969

By Lewis Reeve

As part of a program of investigation of the properties of electric arc welds carried out in the laboratories of the A. 0. Smith Corporation, considerable work has been done on the determination of the oxygen, nitrogen and hydrogen content of different types of weld metal, employing for this purpose the so-called "vacuum fusion method." It is the purpose of this paper to describe certain improvements that have been introduced in this method of determining the gas content of metals, with particular references to the steel specimens examined in this investigation. The method and apparatus used at the beginning of the investigation were essentially those of the Bureau of Standards as described by Vacher and Jordan.' Later a number of changes were introduced which resulted in more rapid evacuation of the graphite crucibles employed and which enabled larger volumes of gas to be dealt with than could be handled conveniently in the Bureau of Standards equipment. In addition, the analyzing of the gases evolved from a melt in the same apparatus as collected was abandoned in favor of analysis outside the equipment using standard methods of gas analysis. The time required for gas analysis in the apparatus itself, as described by the Bureau of Standards, was found to be considerable, and during this time the rest of the equipment was tied up, preventing its use for the analysis of further steel samples. As a result of the modifications introduced, the time required for the analysis of a steel sample for gas content was reduced from about 8 hours to less than 3 hours. Subsequently, the whole procedure of melting the sample and collecting the gases evolved was modified so as to enable a distinction to be drawn between the easily reducible oxides such as iron oxide and the more stable oxides such as silica and alumina. At the same time evidence was obtained indicating the probable existence in the steels of other nitrides than those of iron alone and making possible their quantitative etermination.

Jan 1, 1934

By E. DeGolyer

USE of geophysical methods as an aid to prospecting for new oil pools and in the exploration of already discovered pools continued to increase and reached a new high during 1934. As in previous years, the scene of greatest activity was the Gulf coastal plain of Texas and Louisiana. Seismic crews working by the reflection method increased from some thirty crews at the first of the year to forty crews at the end. An increased demand for torsion balance work at the beginning of the year occurred and practically all available instruments were put into service. Some thirty crews with approximately eighty balances continued throughout the year. Both the pendulum and gravimeter methods of gravity surveys registered their initial successes and equipment was increased from five to seven pendulums and from one to three gravimeters during the year. Approximately five magnetometer parties continued to work throughout the year. No surface surveys by the electrical method are known to have been made. Outside of coastal Texas and Louisiana the chief geophysical work

Jan 1, 1935

By Albert Ledoux

SEVERAL years ago my firm was representing the Mt. Lyell Co. of Australia, which was shipping its blister copper to a refining works in the United States. After the contract had been running for many months, the superintendent of these works discovered that if water was poured upon the surface of the bars much of it would disappear into the interior through blow holes. -Some experiments made by him showed that this could be a considerable amount, so that copper which had been rained on before it was weighed, although the surface appeared dry, nevertheless would contain water. It had frequently occurred in our experience-as samp-lers that the drillings from a lot taken by boring would come out quite wet, and in some cases, indeed, water would drip into the sample pan placed below the bars, due to the fact that the drill had penetrated a cavity or cavities containing water, which presumably got into the cavities at the time the copper was water-cooled after casting, there being, perhaps, no outlet to the surface. So far as I know, until this discovery at the refining works, no. one had thought that rain could penetrate into the interior of blister copper; at least in any quantity sufficient to be considered.

Jan 10, 1922

By Irving B. Cadoff, Stojan M. Zalar

AgInTe2, CuInTe2, and all Proportions of CuxAg1-xInTe, forMed homogeneous single phase alloys after direct solidification from the nielt. X-ray analysis indicated a zinc-blel~de strzccture typical of the chalcopyrite compounds, and the electrical resistivity and Sccbeck coefficient values were in the semiconducting range. AuInTe, and AuxA4g,-, InTe, formed by what appeared to be a peritectic reaction (the thermal analysis curves showing more than one arrest) and were conseyue~ztly polyphase. Substitution of copper into AgIrzTe, resulted in a continuous transition in the room tenzperature Seebeck coefficient from the negative AgIzTe, to the positive CuInTe,. A zero coefficient was obtained at about Cuo.55 Ago.45 InTe, . The temperatzire variation was similar to that observed for the stoichiometric compounds, that zs, tendency towards "p" concEuction at elevated temperatures. The thernzoelectric figure of merit for the compo~uzds, as determined by the Putley -Harmnn method were in the range 10- to 10-7 "K-l; the thermal conductivities in the order of 0.15 cal per sec-cm-oK. INCREASED interest in semiconducting intermetallic substances is expanding much of recent research from simple binary compounds into polyatomic systems and solid solutions. Ternary compounds A' represent a covalent extension of the binary semiconductors Within the a tin isoelec-tronic series, Ag-Cd-In-Sn-Sb-Te-I, divalent cadmium atoms in CdTe are being substituted for by monovalent silver and trivalent indium atoms to form the compound AgInTe, . By cross-substitution with elements of other isoelectronic series, a great number of ternary compounds A 'B"'c? is possible. In all of them, however, a necessary though not sufficient condition for the covalent, semiconducting bond—that there be four sharing orbital electrons per atom—must be fulfilled. In AgInTe,, each silver or indium atom is tetrahedrally surrounded by four tellurium atoms, while each tellurium atom is co-valently bound to two silver and two indium atoms. Synthetic chalcopyrites A'B"'c~ were first recognized as potential semiconduct&rs by Goodman and Douglas.' Austin, Goodman, and Pengelly discuss preparation difficulties and some electronic measurements on AgInS, , AgInSe, CuInSe, , AgInTe, , and CuInTe,. Chalcopyrites A B c2v are mentioned in papers attempting to classify and predict semiconducting behavior of intermetallic compounds; on the basis of saturated tetrahedral sp3 bonds,3 by specific selection criteria,' and by crystallographic considerations."

Jan 1, 1962

One of the results of the work of the Committee on Precious and Base Metals is that the present Bulletin is as large as some of. the annual volumes of Transactions of the Institute, and we extend our. compliments and thanks to the Committee and express to the members thereof and to. the authors, who have so bounteously given of their time and information, the. sincere gratitude of the Institute. In order to get all these papers printed and distributed to the membership in advance of the meeting, it was necessary to divide the work between two printers. This accounts for the discrepancy in the pagination of the Bulletin; and we also ask the indulgence of our readers in case errors have crept into this preliminary edition during the period of unusual pressure. Program of the Butte Meeting.-The program of the Butte meeting will include six technical sessions for the presentation and discussion of papers and five half-clay visits to mines and metallurgical works. The following program is practically in final form, with slight additions which may be necessary later. Every effort will be made to have papers presented and discussed on scheduled time, so that members who are unable to attend the entire meeting may so plan their trip as to hear and discuss papers in which they are especially interested.

Jan 8, 1913

By C. G. Dunn

According to a recently suggested effect of silicon on the re recrystallization textures of high-purity Fe-Si alloys with (111)[112] type rolling textures, the recrystallization texture for a rolled (110)[001] oriented iron crystal probably should be entirely different from that of a (110)[001] oriented 3 pct Si-Fe crystal. Comparative studies of iron and 3 pct Si-Fe crystals, however, show that both have (110)[Ool] recrystallization textures when the rolling textures are the (111)[112] type after reductions in thickness of about 70 pct. Qualitatively the results from the iron crystal are like those of polycrystalline high-purity 3 pct Si-Fe and not like polycrys-talline high-purity iron. The large effect previously noted probably involves unknown impurities or processing variables rather than silicon itself. Some problems on experimental and analytical procedure for a spherical X-ray specimen, which was machined from a laminated composite of sheet specimens, are treated in the Appendix. A possible strong effect of silicon on the textures produced in cold-rolled high-purity Fe-Si (HPFe-Si) alloys during primary recrystallization and normal grain growth was suggested in a recent paper.' All the textures were far from the random-orientation type, but that of iron, or of Fe-Si alloys of low silicon composition, was entirely different from the texture of 3 pct Si-Fe. The same effect was noted for the textures obtained prior to normal grain growth, i.e., for primary recrystallization.2 It is the main purpose of the present paper to provide some clarification of this silicon effect. All the HPFe-Si alloys from zero to 3 pct Si, which were rolled by two or more stages separated by anneals, developed (111)[112] type rolling textures.2 Thus, there was no effect of silicon on the rolling textures. Earlier, Gensamer and Mehl3 also found no effect of silicon on the rolling textures of Fe-Si alloys; they obtained the Kurdjum.ow and Sachs (K-S) rolling texture for iron,4 which is characterized as the three ideal components: (100)[011], (112)[li0], and (111)[112]. There is a difference between the HPFe-Si multiple-stage rolling texture and the K-S single-stage rolling texture, but this is a variable processing effect. Of interest here is the fact that the recrystallization textures from (111) [llZ] type rolling textures were different depending on the amount of silicon in the alloy. There was a relatively strong (110) [001] component in the recrystallization texture of HP 3 pct Si-Fe5,8,2 but no such component in HP 0.6 pct Si-Fe, for example; the recrystallization texture for the latter was two (111) [110] type components and a (111) fiber component 1,2 Several publications have shown that a strong (110) [001] recrystallization texture is derivable from a (111) [112] type rolling texture for 3 pct Si-Fe crystals reduced in thickness by about 70 pct.7-10 Furthermore it appears that the strongest of these (110) [001] recrystallization textures occurred when the orientation of the crystal prior to rolling was (110) [001].7 Barrett and evensoon11 found that the rolling texture of a (110)[001] oriented iron crystal was (111) [llj]. Accordingly, it seemed desirable to determine whether a (110) [001] oriented iron crystal, upon rolling and annealing, would behave like the 3 pct Si-Fe crystal (or the polycrystalline HP 3 pct Si-Fe) and thus produce a (110) [001] recrystallization texture contrary to the suggested silicon effect, or would behave like the polycry stalline HP iron or HP 0.6 pct Si-Fe and thus produce (lll) [110] type components in agreement with a silicon effect. Briefly, the idea here involves the use of more precisely defined textures to obtain if possible better control of important variables that affect the recrystallization process. PROCEDURE A (110) oriented crystal of Ferrovac "E" iron (99.9 pct pure) was prepared in sheet form 0.080 in. thick with the [001] direction parallel to the long dimension of the specimen.'' This crystal was etched to 0.073 in. thickness (to remove some small included grains) and then was cold rolled in a 6-in.-diam mill to a final thickness of 0.022 in. The rolling was unidirectional except for an inadvertent reversal at 0.061 in. thickness. At this thickness, and also at 0.040 in., the rolling was interrupted for transmission Laue photographs. Molybdenum Ka-radiation filtered with zirconium was used in a transmission method1' to obtain the cold-rolled (110) pole figure. The sample was a 0.002-in.-thick section taken from the central region of the 0.022-in.-thick cold-rolled crystal. For the primary recrystallization study, cold-rolled samples were etched from 0.022 to 0.021 in. thick and annealed in hydrogen at 850°C. Primary recrystallization to a fine-grained structure, Fig. 1, was obtained in a 5-min anneal. Eleven sheets after

Jan 1, 1963

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.' In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.' This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,' electrochemical potential,8 time lag,' and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda's result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.' MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By J. L. Gregg

RECENTLY there has been considerable interest in the production and use of, extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wire-drawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names. No performance data are given and no inference as to the inferiority of one alloy as against any other is made K Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification.

Jan 1, 1929

The General Committee met in the Treasury Building at Washington on Oct. 6 and 7. At the first meeting, Cornelius P. Kelley was appointed chairman, and Paul Armitage, secretary. Sub-committees were ap-pointed on Invested Capital, Mine Valuation, and Depletion and De-preciation. On Oct. 7, the reports of these committees were submitted to the General Committee and were referred to the Executive Committee. A motion was carried that the Executive Committee he constituted a permanent committee to continue the work of the Committee, with full power to acid to and increase its membership, that. as thus increased, it should constitute a permanent organization to act- and cooperate with the Treasury Department in matters of mining taxation under the Federal Income and Excess Profits Tax Laws. Thereafter the Executive Com-mittee met and formed a permanent committee as follows: Cornelius F. Kelley, chairman, 42 Broadway, New York City. J. L. Darnell, office of the Commissioner of Internal Revenue, Wash-ington, D. C. J. Parke Channing, 61 Broadway, New York City. Walter Douglas, 99 John St., New York City. R. V. Norris, 542 Second National Bank Bldg., Wilkes-Barre, Pa. J. E. Spurr, Engineering and Mining Journal, 10th Ave., and 36th St., New York City. W. G. Swart, 808 Selwood Bldg., Duluth, Minn. J. P. Finley, 45 Cedar St., New York City. W. A. Williams, Bartlesville, Okla. F. S. Peabody, Peabody Coal Co., McCormick Bldg., Chicago, Ill. Matthew C. Fleming, 71 Broadway, New York City. H. B. Fernald, 54 Wall St., New York City. William G. Mather, Cleveland, Ohio. Walter Fitch, Eureka, Utah. Arthur Thacher, 900 Security Bldg., St. Louis, Mo. John P. Gray, Coeur d'Alene, Idaho. Paul Armitage, secretary, 233 Broadway, New York City.

Jan 12, 1919

By C. F. Frey, P. J. Ahern, J. F. Wallace

THE high affinity of molten titanium for oxygen and nitrogen has resulted in considerable difficulty in developing a satisfactory melting procedure. It has been found necessary to perform melting operations either in a vacuum or inert atmos-phere, and failure to obtain a satisfactory crucible material has necessitated the use of special melting techniques. These techniques have included cold-mold arc-melting utilizing both consumable and nonconsumable electrodes, skull-melting, drip-melting, and levitation melting.' It has been recognized generally that the melting of both titanium sponge and titanium scrap would be expedited by the use of induction-melting procedures but the lack of a crucible capable of containing molten titanium without objectionable contamination thus far has prevented the use of induction-melting procedures. An extensive investigation: which included the common refractory materials was not successful in developing a satisfactory crucible for induction-melting. Some success in induction-melting has been attained with the use of a graphite crucible material, but in all instances sufficient carbon contamination was encountered to cause an appreciable reduction in the optimum mechanical properties of the titanium or titanium alloys. These investigations"" report an increase in the carbon content from approximately 0.3 to 1.0 pct. A serious reduction in the tensile and forming properties has been observed as a result of this carbon contamination. The development of a satisfactory induction-melting procedure for titanium without undue contamination undoubtedly would have considerable economic significance. Such a process would be particularly useful in melting the large quantities of low-cost scrap now available that can only be reprocessed at considerable expense and difficulty by the more elaborate techniques referred to previously. In addition, the process could provide a satisfactory method of melting and alloying of bri-quetted sponge for forging ingots.

Jan 1, 1959

By E. R. Gilbert

Klopp et al. have reported data on tensile and creep properties of are-melted and electron-beam-melted tungsten. We would like to point out some similarities between their creep results and ours on are-melted and powder-metallurgy tungstenand offer some alternate interpretations of the data which lead to different rate-controlling mechanisms. Klopp et al. observed extensive transient creep in the 2250" to 3500°F temperature range where the acthetivation energy is 106,400 ± 3300 cal mole-1. They suggest cross slip as the possible rate-controlling mechanism since "cross slip may occur only by the movement of screw dislocations, and not edge dislocations, thus allowing only partial recovery of the strain hardening and resulting in a continuously decreasing creep rate, characteristic of transient creep.'' Our tests on are-melted tungsten and powder-metallurgy tungsten displayed an extensive transient creep stage in the same temperature range but they also displayed a steady-state creep stage. The stress levels and strain rates of the two investigations, 1.4 to 7 kg mm-2 and 10-7 to 10-4 sec-1 for that of Klopp et al. and 4.5 to 10 kg mm-2 and 10-8 to 10-4 sec-1 for those of Gilbert et al., are overlapping. The activation energy for creep of our powder-metallurgy tungsten is 105,000 cal mole-1. This close agreement with the value found by Klopp et al. suggests that the same mechanism may be common to both types of materials. It may be possible to gain some additional insight into the rate-controlling mechanism by applying the analysis made by conrad22 in terms of the activation volume. The value for the activation volume depends upon the dislocation mechanism and may be used to help differentiate between various dislocation mechanisms. The activation volume for cross slip is 10 to 100 b3. Values determined from our data were 130 to 220 b3 which are in better agreement with the range of 102 to 104 b3 for nonconservative motion of jogs. Values determined from data of Klopp et al. are 240 to 1040 b3. We suggest that the rate-controlling mechanism for creep in this temperature range may be nonconservative motion of jogs assisted by enhanced diffusion along grain boundaries or dislocations. This model requires an activation energy lower than that for self-diffusion as is observed. If this is the controlling mechanism, a higher activation energy which is closer to that for self-diffusion might be expected for tests conducted on specimens with reduced grain boundary area, i.e., larger grain size. In support of this premise we have conducted tests on speci- mens having one to three grains per cross section for which a higher activation energy of 130,000 cal mole-1 was observed. Also, in agreement with results of Klopp et al., a faster creep rate resulted from the increased grain size and probable decreased dislocation density. Further argument against the cross slip mechanism is based on the constant activation energy we obsserved over the range of 5.0 to 10 kg mm-2,21 whereas the activation energy for cross slip displays a significant stress dependence.23 In addition to this, the powe on the stress term for the strain-rate dependence appears too high for cross slip. The values for tungsten fall in the range of 4.5 to 7 (Klopp et al. and Ref. 21) whereas values of approximately 2 are observed in creep by cross slip for hep metals.24 At temperatures from 3300° to 4000°F, Klopp et al. observed an activation energy of 141,000 ± 4000 cal mole-' which is less than that for self-diffusion, 153,000 cal mole-1, 25 and less than that reported for high-temperature creep of powder-metallurgy tungsten by Green:' 160,000 cal mole-1. Klopp et al. suggested that recovery of strain hardening by dislocation climb is the rate-controlling mechanism in this temperature region. Actually an activation energy larger than that for self-diffusion is predicted by this model if the temperature dependence of the elastic modulus27 is taken into consideration. Klopp et al. attributed this lack of correlation to the compositional differences between powder-metallurgy tungsten used by Green and their own arc- and EB-melted tungsten. It is our position that the value of 141,000 ± 4000 cal mole-' represents a transitional value between the higher and lower activation energies and does not represent a discrete mechanism of deformation. If the tests had been extended to higher temperatures the higher value of activation energy would have been observed as has been demonstrated by both our analy sis'' of isothermal test data by GE-NMPO28 and differential temperature tests28 on are-melted tungsten. The activation energies determined (170,000 and 160,000 cal mole-1) were greater than that for self-diffusion and are in better agreement with the value found by Green. The model of dislocation climb is associated with ; activation volume of 1 b3 according to Conrad.22 The activation volume calculated for the creep data of fou independent investigators in the temperature range where the activation energy for creep is near that for self-diffusion (Klopp et al. and Refs. 26, 28, and 30) is 110 to 2800 b3 and is in the range suggested for nonconservative motion of jogs. In the case of tungsten this mechanism may be preferred over that of dislocation climb. Sincere appreciation is expressed to Messrs. J. E. Flinn and F. L. Yaggee for the helpful discussions and suggestions in the preparation of this communication.

Jan 1, 1967

By John A. Church

In the year 1874, when the price of pig-iron was still high, that staple product became the subject of discussion in the newspapers and among those philosophers who are determined to know the "reason why" for all things. The object of the inquiry was to find out Why iron did not fall in price as much as some other things had fallen. Indeed, there seemed to be an impression that iron and gold ought to move on nearly parallel lines, for the fact was constantly brought forward that iron then cost twice as much as it did before the war, though gold had returned to within twelve or fifteen per cent. of its former value. After some time the papers, by what seemed to be nearly unanimous consent, reached the conclusion that the maintenance of high prices was the work of the furnace proprietors, who, as the result of their shrewdness, were pocketing enormous profits. No proof was given to support this opinion, and the figures of cost and sale that were produced were of the most general kind, and used in the most vague manner. Visiting the president of the Thomas Iron Company, whose great works at Hokendaqua and Catasauqua, in Pennsylvania, are so well known as the largest and among the best conducted in America, I found him quite willing to meet the vague suspicions of the newspaper wiseacres, by a publication of the figures contained in the furnace-books of his company. These were accordingly given to the world through the Engineering and Mining Journal, and attracted the general attention they so well deserve. Though my own name became connected with these statistics, from the fact that I used them as the basis for the first attempt ever made to calcalate the furnace economy of an American works, I can, without the suspicion of egotism, say that the statistics referred to are the most valuable contribution the literature of American blast-furnace work has yet received, for their interest is independent of personal considerations, and due entirely to the fact that they represent faithfully the details of practice in one of the most prominent American works. They are an exact transcript of the furnace-books, and form a body of accurate information of the greatest value to the metullurgical student. Their importance is shown by the fact that though the theoretical conclusions which I based upon them have been several times attacked, not one of my critics has made the slightest contribution to

By John A. Church

IN the year 1874, when the price of pig-iron was still high, that staple product became the subject of discussion in the newspapers and among those philosophers who are determined to know the "reason why" for all things. The object of the inquiry was to find out why iron did not fall in price as much as some other things had fallen. Indeed, there seemed to be an impression that iron and gold ought to move on nearly parallel lines, for the fact was constantly brought forward that iron then cost twice as much as it did before the war, though gold had returned to within twelve or fifteen per cent. of its former value. After some time the papers, by what seemed to be nearly unanimous consent, reached the conclusion that the maintenance of high prices was the work of the furnace proprietors, who, as the result of their shrewdness, were pocketing enormous profits. No proof was given to support this opinion, and the figures of cost and sale that were produced were of the most general kind, and used in the most vague manner. Visiting the president of the Thomas Iron Company, whose great works at Hokendaqua and Catasauqua, in Pennsylvania, are so well known as the largest and among the best conducted in America, I found him quite willing to meet the vague suspicions of the newspaper wiseacres, by a publication of the figures contained in the furnace-books of his company. These were accordingly given to the world through the Engineering and Mining Journal, and attracted the general attention they so well deserve. Though my own name became connected with these statistics, from the fact that I used them as the basis for the first attempt ever made to calculate the furnace economy of an American works, I can, without the suspicion of egotism, say that the statistics referred to are the most valuable contribution the literature of American blast-furnace work has yet received, for their interest is independent of personal considerations, and due entirely to the fact that they represent faithfully the details of practice in one of the most prominent American works. They are an exact transcript of the furnace-books, and form a body of accurate information of the greatest value to the metallurgical student. Their importance is shown by the fact that though the theoretical conclusions which I based upon them have been several times attacked, not one of my critics has made the slightest contribution to

Jan 1, 1876

By T. S. Jr. Sligh

OF all the qualities that are essential in a good cigar tobacco none is quite so important as the burn. This term is general and includes many points, the most important of which are evenness of burn, color of ash, firmness and coherence of ash, and fire-holding capacity. The fire-holding capacity refers to the length of time the leaf or cigar will continue to, glow after ignition. Chlorides tend to prevent complete combustion and products are formed thereby that are injurious to the flavor and aroma. On the other hand, the carbonates of the alkalies, particularly of potassium, aid the combustion and increase the fire-holding capacity. Barth1 thought that the harmful effect of the chlorides was due to their fusing and coating the tobacco, thereby preventing complete combustion. Schlosing,2 Nessler,3 and Garner,4 suggested widely different theories to account for the favorable action of potassium salts. In order to study carefully the action of the various salts upon the course of combustion of the cigar a knowledge of the temperature of the burning cigar is necessary. Lehmann5 who seems to be the only investigator who has made any attempt to determine the temperature of a burning cigar gives 480° C. as the maximum temperature which he recorded. It is evident, however, that his measurements were in error, probably on account of the method and apparatus used, since the lowest visible red corresponds to a temperature of about 575° C.

Jan 9, 1919