Search Documents

By AIME AIME

THE autumn is the time that nearly all the special groups within the broad field of the Institute's activitives chose for their own special meetings. The big annual meeting in New York in February has its own special advantages, but to realize them involves sacrificing others. A meeting of a smaller group with the subjects brought up for discussion much more closely limited to a single field of interest has some advantages that a big general meeting cannot possibly have. And so the custom has gradually developed of having these smaller meetings in the autumn, at con¬venient places, so the men will not have to travel too far from the job to be present. Sometimes the meetings have for their field of interest a single phase of mineral technology, and are called divisional, and at other times they cover a diversity of topics that are locally important in that geographical area, and are then called regional meetings. Of the five meetings to be held this fall, four are divisional and one regional. Two of the divisional meetings are to be held in the same place at the same time, but with programs so arranged that they do not conflict.

Jan 1, 1930

H. W. Turner, San Francisco, Cal. (communication to the Secretary*): This excellent paper apparently represents the results of extensive observation and experience among the mines of the Mother-Lode, but I strongly question its relegation of the dioritic intrusions to the period of fissuring and ore-deposition. The dioritic rocks referred to are evidently those areas represented by Ransome in the Mother-Lode folio1 as meta-diorites, and, as he says, are merely basic facies of the great granodiorite batholite of the Sierra Nevada. If followed downward I venture to predict that these meta-diorite areas would be found to connect with the great batholite, and to be in fact mere apophyses of it. I see no reason for supposing that these apophyses were intruded into the Mother-Lode slates at a period later than the intrusion of the granodiorite in general. The period of fissuring was subsequent to this intrusion; the basic granodiorite or quartz-diorite areas of the foot-hill region are themselves fissured extensively; and the fissures were filled with quartz, apparently during the same general period of the formation of the Mother-Lode veins. Prichard and Ransome2 both refer to the deposition of quartz in the same lode at different periods resulting from a reopening of the fissures. Some time since, I saw in the stopes of the

Jan 1, 1904

By Morton Macartney

FOR many years the developers or owners of worthy mining ventures in need of financing have found it almost impossible to obtain such financing under the conditions existing in most other lines of business. High rates of interest and unfair participation in profits have robbed the developers of much of their holdings, and have resulted in over-capitalization and many other like evils. When the general financial condition of the country is bad, this difficulty increases to a point where many operations must cease and hen are thrown out of employment. In 1.934 this situation had developed to such a point that Congress attempted to aid the mining industry. It first authorized the RFC to make loans to recognized and established corporations, individuals, and partnerships engaged in the business of mining, milling, or smelting of ores in June, 1934, limiting such authority to loans adequately secured, the security to consist of mineral acreage. The requirements of the law were stringent and of the 252 requests for loans received up to June 1, 1935, 35 were authorized.

Jan 1, 1936

THE third annual Joint Western Mining Convention, held at Los Angeles, Sept. 10 to 13 inclusive, was a notable success both as to attendance and interest. Registration the first day amounted to 201, and the total crept up to 347 before the close. The American Institute of Mining Engineers was well represented, approximately 80% of those registered and most of the speakers being members. This illustrates largely the amount of interlocking membership and the reason for holding at one time and place meetings of the several related organizations. The plan has proved so successful that it is probable that Spokane will extend an invitation for next year that seems likely to be accepted. It is proposed that the convention be timed so as to permit visitors from the East to stop there Oct. 3 to 5, en route to the American Institute of Mining Engineers meeting at San Francisco, Oct. 7 to 9. Simultaneously, it is expected that the Petroleum Division will hold its fall session at Los Angeles, the two streams of travel meeting in San Francisco, just before departure of the party of engineers traveling to Japan to attend the World's Engineering Congress. The Los Angeles meeting opened Monday morning with a general session under the auspices of the Western Division of the American Mining Congress with Philip Wiseman in the chair. After a series of short responses to the welcome extended, Charles W. Merrill discussed the needs of the western mining industry. A complimentary luncheon to members and delegates followed.

Jan 1, 1928

By W. R. Hansen, F. W. Boulger

Twenty-nine laboratory steels were studied to determine the effects of composition and ferrite grain size on drop-weight and Charpy V-notch transition temperatures. The experimental steels covered the following ranges in composition.. 0.10 to 0.32 pct C, 0.30 to 1.31 pct Mn, 0.02 to 0.43 pct Si, md nil to 0.136 pct acid-soluble Al. Although most of the data were obtained on hot-rolled samples, some plates were heat-treated in order to cover a wider range in ferrite grain size. The experimental data were used for a multiple-correlation analysis conducted with the aid of an electronic computer. The study showed that carbon raises and that manganese, silicon, aluminum, and finer ferrite grains lower both drop-weight and Charpy transition temperatures. Quantitatively, variations in composition and grain size have a more marked effect on V15 Charpy transition temperatures than on the drop-weight transition temperature. Useful correlations were found between transition temperatures in drop-weight tests and those defined by seven different criteria for Charpy tests. Evidence was accumulated that the conditions ordinarily used for drop-weight tests are more severe for 1-1/4-in. -thick plate than for 5/8- to 1-in. -thickplate. PROJECT SR-151, to study quantitatively the effects of metallurgical variables on performance in the drop-weight test, was established by the Ship Structure Committee late in 1958 on recommendation of the National Academy of Sciences, National Research Council. This project was initiated as a result of the increasing use of the drop-weight (nil-ductility) test in predicting the ductile-to-brittle behavior of steel. Qualitative data indicated the drop-weight was not as sensitive to metallurgical variables as the Charpy V-notch test. Furthermore, the available information indicated that the drop-weight test did not show the superiority of killed steels over semikilled steels reflected by Charpy tests. This difference in sensitivity to brittle fracture is considered important because the drop-weight transition temperature has been reported1 to correlate better with service-temperature failures than the V-notch test does at a constant energy level. Therefore, this project was concerned with establishing quantitatively the effects of metallurgical variables in the drop-weight test. For comparison, Charpy V-notch data were obtained for the steels investigated. This paper summarizes the results of the investigation. Most of the steels used for the study were made and processed in the laboratory. However, some tests were also made on commercial killed steels available from Project SR-139 (SSC-141). During the course of the investigation, data were obtained on the effects of carbon, silicon, manganese, and aluminum on transition temperatures of drop-weight and Charpy specimens. In addition, the effects of heat treatment which changed the ferrite grain size and the transition temperatures were also investigated. Finally a few exploratory studies were made on commercial killed steels to evaluate the effects of plate thickness, grain size, and heat treatment on the performance of drop-weight specimens. EXPERIMENTAL PROCEDURES Preparation of Materials. A total of twenty-nine 500-lb induction-furnace heats were made and processed in the laboratory for the investigation. Carbon, manganese, silicon, and aluminum contents were systematically varied. Melting and rolling techniques proven satisfactory in a previous project2 were used as a guide for the current investigation. Composition. The composition of the twenty-nine laboratory heats made for this project are given in Table I. The steels are divided into three groups. The first group consists of ten aluminum-killed steels similar in composition to Class C ship-plate steel. The second group consists of ten semikilled or Class B type steels. In both of these groups the carbon and manganese contents were intentionally varied over a wide range. This wide range in composition was helpful in obtaining quantitative data from a limited number of steels. The primary purposes of these two groups of steels was to determine the effects of carbon, manganese, and deoxidation practice. In addition, one steel in each group (Steels 2-2 and 9-2) were made about 1 year after the start of the program in order to check consistency of melting practice. The third group of nine steels listed in Table I was intended for studies on the effects of silicon and aluminum. In eight of these steels carbon and manganese were held relatively constant at levels of about 0.2 and 0.8 pct, respectively, while silicon and

Jan 1, 1963

By C. R. Kuzell

The Editor desires to call attention to the charts in the paper of the above title which were published in the August Bulletin on pages 2190 and 2191. It was impracticable to include in the Bulletin. charts of sufficient size to be used as working diagrams for the direct determination of operating values, but the Institute is prepared to furnish copies of these charts on a large-size scale, at a moderate cost, to those who desire to have them for this purpose. CORRECTIONS Page 2185, line 3. For "is accessory apparatus" read "in accessory. apparatus." Page 2188. Substitute for lines 11 and 12: Nitrogen, oxygen, carbon monoxide, Cp = 6.50 + 0.0010T Hydrogen, Cp = 6.50 + 0.0009T

Jan 9, 1914

By Edwin T. Wood

THE term blending as used herein refers to the mixing of ores assaying more than 0.20 pct U3O8 with low grade material assaying less than 0.20 pct U3O8. Such blending when properly understood and controlled will produce more total dollars of profit from many mining ventures. The question whether or not to blend is particularly vexing when an orebody is surrounded by an envelope of low grade material or separate tonnages of low grade exist which could be extracted coincident with the higher grade ores. Should any, all or part of this low grade be mined? If so, in what proportion and what is the limiting assay of the low grade material?

Jan 7, 1958

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500' and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,' in the a Fe-Fe3C system are those of Bannyh, Modin, and odin' for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.'-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3'C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.' Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By Eckhard Nembach

The phase diagram of the system Pb-In has been investigated between -27° and + 40°C, using nzainly X-ray dijfraction. In accordance with t her mo dynamic measurements by Heumann and Predel, a segregation occurs at low temperatures, though not in the form of a nziscibility gap. THE phase diagram of the system Pb-In has been the subject of extensive investigations,1&apos;1 but recently Heumann and prede13 concluded from their thermodynamic data that a new feature should occur below room temperature. These authors observed that the maximum values for the enthalpy and entropy of mixing, which occurred at a composition of 50 at. pct Pb, were +400 and —1.7 cal per g-atom deg, respectively. From this the authors estimated that a miscibility gap should occur below 30°C, centered at 50 at. pct Pb. Resistivity measurements seemed to support this view. These authors proposed the phase diagram outlined in Fig. 1. Three phases exist at 30°C: the tetragonal indium phase with c/a > 1, the tetragonal intermediate phase a, with c/a < 1, and the fcc lead phase. During an investigation of the superconducting properties of Pb-In alloys. it has been observed4 that aging a specimen with 50 at. pct Pb for 14 days at -18°C decreased the superconducting transition temperature about 0.13"K and tripled the transition width. In this paper, the results of an investigation of the Pb-In phase diagram in the temperature range from — 2T to +40°C are reported. Superconductivity and X-ray methods have been used. 1) SPECIMEN PREPARATION The materials were provided by the American Smelting and Refining Co. According to the manufacturer their purity was 99.999 pct. The weighed amounts of the constituents were sealed in quartz tubes under an atmosphere of 10 torr helium, mixed for 24 hr in a rocking furnace at 380°C, quenched in ice water, and homogenized at 20" to 30°C below the solidus line, established by Heumann and Predel. The annealing times were 144 hr for specimens containing Less than 30 at. pct Pb and 36 hr for the remainder. 2) SUPERCONDUCTIVITY EXPERIMENTS The specimens were quenched from the homogeniza-tion treatment into ice water and their superconducting transition temperatures T, measured. The procedure used has been described in Ref. 4. The transition was detected by the change of the mutual induc- tance of two coaxial coils containing the sample. T, was defined as the temperature at which 50 pct of the total change in inductance had occurred. The repro-ducibility with which T, could be measured was i0.002"K. Then the specimens with lead contents between 38 and 75 at. pct were aged for 7 days at temperatures between -30" and 40°C. If this treatment caused T, to change by more than 0.005"K or the width of the transition to increase by more than 0.002"K, it was concluded that the specimen had undergone a phase change and no longer consisted only of the fcc lead phase: as it did immediately after homogenizing. The result is shown in Fig. 2. From this one can estimate at what temperatures and concentrations phase changes occur. The X-ray measurements were based on these preliminary results. 3) X-RAY EXPERIMENTS Because of the softness of the material, relatively coarse powders. 75 p, had to be used, which were filed in a helium atmosphere from homogenized specimens. The powders were annealed at least 30 min at temperatures between 120" and 16OJC, depending on their concentration, and quenched in ice water. Then their X-ray patterns were taken at -178°C with a Picker diffractometer, model 3488K, and a cold stage. on which the specimen was in thermal contact with a liquid-nitrogen reservoir. In this way the following relation was established for the fcc lead phase: a = 4.697 + 0.00247C for 40 5 C 5 75 11 where n is the lattice constant (A) and C is the at. pct of lead. The coarseness of the powder made it impossible to use lines with 0 > 75 deg; therefore n was averaged from lines with 45 deg 5 0 5 75 deg. The results were reproducible to within i0.05 pct. Relation [I] is very similar to the one found by Heumann and Predel at room temperature. Following this, homogenized specimens with compositions between 15 and 56 at. pct Pb were aged for at least 10 days at temperatures between -27" and

Jan 1, 1970

By K. E. J. Rapperport, C. S. Hartley

The only slip system observed in zirconium crystals deformed at 77", 575", and 1075OK was (1010) [1210] with a critical resolved shear stress in tension of 1.0 kg per sq mm at 77°K; 0.2 kg per sq mm at 575 °K; and 0.02 kg per sq mm at 1075 OK. The active twin planes were {1012}, (1121}, (11221, and (11233) with varying temperature dependence. A detailed analysis for the slip direction using Laue spot asterism is appended. NeARLY all metals of the hexagonal close-packed structure exhibit basal slip, i. e.,(0002)<1120>- type slip. This is true of magnesium,&apos; zinc,&apos; cadmium,3 beryllium,4 titanium,= yttrium,6 and rhenium.Many of these such as titanium 5&apos;8-&apos;0beryllium,4&apos;" magnesium, and zinc13&apos;14 display other slip modes even at room temperature, and nearly all have been reported to slip on other systems under particular loading or temperature conditions of testing. As is shown in this paper, basal slip was not found at any of four test temperatures from 77" to 1075°K in hexagonal close-packed zirconium under the simple loading conditions of tension and compression, even though in one case the resolved shear stress on the inactive (0002) <llgO> system was twenty-five times higher than the critical resolved shear stress on the active (1010) [1210] system. This result is consistent with prior studies on the active deformation processes in zirconium deformed at room temperature. &apos;&apos;-I7 SPECIMEN PREPARATION A) Material—The zirconium used in this work was of two types: 1) as-deposited reactor grade crystal-bar, and 2) arc-melted and forged reactor grade crystal-bar. Typical chemical and spectrographic analyses of these materials as received, and after hydrogen removal and crystal growth are given in Ref. 17. Crystals of type 1) above have the letter prefix (A) and those of type 2) have the prefix (B) throughout this paper. B) Crystal Growth— he zirconium was machined into rectangular parallelepipeds about 0.2-in. scl in cross section and 2 in. iong. These were hand polished through 4/0 abrasive paper, electropolished, given a hydrogen removal anneal, and subjected to long-time anneals at 840 °C in vacuo to produce usable crystals.&apos;7 A second technique used to obtain large crystals was to cycle the samples two or three times between 1200" and 840°C, allowing them to remain at the higher temperature for about 4 hr and at the lower temperature for 5 days.17 These techniques yielded some grains which occupied the entire cross section of the bar and were as long as 3/4 in. C) Orientation Determination—After the growth of large crystals by thermal cycling, the samples were repolished with extreme care through 4/0 abrasive paper and electropolished. Metallographic examination after polishing showed the surfaces to be free of visible deformation traces. Standard Laue back-reflection X-ray techniques were used to find the crystallographic orientations of selected large grains with respect to a specimen face and edge. Fig. 1 shows the stereographic projections of the stress axes for the crystals used. The sharpness of the spots on the Laue photographs indicated that the crystals were of good quality. EXPERIMENTAL METHODS Nine crystals were deformed in tension at 77"K, nine in tension and five in compression at 300°K in previous tests,17 fifteen in tension at 575"K, and eleven in tension at 1075°K. All specimens were stressed by load increments. After a predetermined load was applied, the specimen was removed from the loading appratus and metallographically examined for deformation traces. An attempt was made to initially stress each bar so that some crystals slipped a small amount and others not at all. This was done to bracket the critical resolved shear stress. One bar of special orientation (B-11) was repolished and annealed at 1075°K for 1 hr after lower temperature deformation, before final deformation at 1075°K. In the other bars the loading by increments, followed by metallographic examination, was continued until the surface distortion would interfere with analysis, or until fracture. One example of a crystal pulled to fracture is shown in Fig. 2. This photograph shows a crystal (B-14C) which was pulled at 1075°K and failed by slip on two (10i0) planes. The approximate orientation of this crystal is illustrated in the figure. Specimens were deformed at 77°K in liquid nitrogen on a tensile machine using an insulated bucket with an internal hook to accept a clamped specimen.

Jan 1, 1961

By G. K. Manning, A. R. Elsea, C. R. Simcoe

Boron increases the hardenability of hypoeutectoid steels by decreasing the nucleation rate of ferrite and bainite. It is postulated that concentrations of lattice imperfections, such as exist at the grain boundaries, furnish the necessary energy for nucleus formation. Boron, because of its atomic diameter, will concentrate at lattice imperfections where sites of suitable size are present. Boron will decrease the energy of these local areas by occupying these sites. This mechanism accounts for the large increase in hardenability observed with small amounts of boron. The loss of the boron hardenability effect and the boron precipitate formation are explained on the basis of increased concentration of boron at the grain boundaries either with increasing boron content of the material or with increasing temperature. COMMON alloying elements affect both the nucleation and growth rates of the austenite decomposition reactions.&apos; This effect is largely a result of the slow diffusion rates of these elements. Although a small addition of boron markedly increases the hardenability of steel, the diffusion rate of boron, which is of the same order of magnitude as that of carbon, can hardly account for this effect. An addition of boron in the range of 0.001 to 0.003 pct is about as effective as an addition of 0.30 pct Mo, 0.40 pct Cr, or 1.25 pct Ni in increasing the hardenability of a 0.40 pct C steel;&apos; however, increasing the carbon content of the steel decreases the effectiveness of the boron addition."&apos; The difficulty in understanding why so small an addition of boron can replace much larger quantities of the more strategic alloys, together with the erratic behavior sometimes encountered in boron-treated steels, has interfered with their general acceptance by industry. In the belief that an understanding of the mechanism by which boron increases the hardenability of steel should lead to a more general acceptance of boron-treated steels, a research investigation to determine this mechanism was undertaken at Battelle Memorial Institute under sponsorship of Wright Air Development Center. Experimental Work In order to study the effect of boron on the transformation of austenite to ferrite and bainite, a group of steels was made with a basic composition similar to that of the SAE 8600 series. This base composition was chosen because it has sufficient hardenability to permit accurate measurement of the times required for transformation to start at various temperatures. The chemical analyses of the steels used in the first part of this investigation are listed in Table I. These steels were made as 200 lb heats in an induction furnace. The furnace charge was Armco ingot iron with the alloying elements added as ferroalloys. After the alloy additions were made, the heat was deoxidized with 0.125 pct Al. A 100 lb ingot was cast and an addition of 0.003 pct B, as ferroboron, was made to the metal remaining in the furnace. This metal was cast into a second 100 lb ingot. The ingots were forged to 11/4 in. diam bar stock from which end-quench hardenability specimens were obtained. Part of this material was further reduced by hot rolling to lx¼ in. bar stock from which specimens were obtained for isothermal transformation studies. Studies of Nucleation and Growth: End-quench hardenability tests were performed on these steels, using an austenitizing temperature of 1600°F. The hardenability curves, shown in Fig. 1, indicate that boron treatment resulted in considerable increase in hardenability of the steels. Any such change in hardenability must result from a change in the transformation rate of the austenite, and these rate changes can be established readily by isothermal transformation studies. Isothermal transformation studies were conducted on these steels as follows: specimens were austeni-tized at 1600°F for 15 min, transferred to a lead bath operating at a constant subcritical or intercritical temperature, held for various lengths of time, and water quenched. The specimens were sectioned for metallographic examination to determine the amount and the type of transformation products present. In order to determine the effect of boron on the formation rate of ferrite, isothermal transformation tests were made on the 0.20 pct C steel in both the boron-treated and boron-free condition at an intercritical temperature of 1375°F where ferrite is the only decomposition product of this low carbon austenite. The results of these tests are shown in Fig. 2, where the percentage of ferrite formed is plotted as a function of time at temperature. It is apparent that boron markedly decreased the transformation rate of austenite to ferrite at this temperature.

Jan 1, 1956

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By F. V. Lene, E. J. Westerman

The recrystallization behaviors of two extruded and cold-drawn experimental sintered aluminum powder alloys, containing 1.75 and 3.0 pct Al2O3 by weight, were compared with that of extruded and cold-drawn commercially pure alumirzum. The kinetics of recrystallization of the alloys are described semiquantitatively. For the alloy containing 1.75 pct A l203 the rates of nucleation and of growth were also semiquantitatively determined. THE most striking property of aluminum alloys strengthened by a dispersion of Al2O3, the so-called SAP alloys, is their stability at elevated temperatures. One of the manifestations of this stability is their resistance to recrystallization after they have been cold worked. Most of the commercial grades of either the Swiss SAP or of Alcoa&apos;s Aluminum Powder Metallurgy Products have not been recrys-tallized after cold working, even when they are heated for a long time at a temperature near the aluminum melting point. Lenel, however, observed that the dispersion strengthened aluminum alloys with a larger spacing between the oxide particles than that of most commercial grades would recrys-tallize.1 It appeared to be of interest to further investigate the mode and kinetics of recrystallization of these alloys, and to compare their recrystallization behavior with that of commercially pure aluminum. Because homogeneous deformation of these SAP alloys in tension did not provide sufficient cold work to induce recrystallization, they were cold worked by wire drawing; the nonuniformity of this deformation unavoidably complicated the interpretation of the recrystallization studies. EXPERIMENTAL DETAILS Extrusions—Two types of sintered aluminum powder extrusions were used in this study. One type, designated AT-400, was produced from Reynolds atomized aluminum powder consisting of spherical particles averaging 3µ in diam and containing 1.75 wt pct of Al2O3. This powder was very similar to the R3M powder from which extrusions were previously prepared with an average spacing of 0.9µ between oxide particles.2 The second type, designated MD 2100, was produced from Metals Disintegrating Co. flake powder containing 3.0 wt pct of Al2O3, with an average flake thickness of 0.8µ. The average spacing between oxide platelets in MD 2100 extru- sions was 0.45µ.2 Powder compacts of 3/4-in. diam were extruded at 1000°F into 0.097-in. diam (AT-400) and 0.093-in. diam (MD 2100) wires by methods previously described.3 In order to compare the recrystallization behavior of sintered aluminum powder extrusions with that of wrought commercially pure aluminum 3/4 in. rod stock of 1100 F aluminum was extruded at 1000°F into 0.102-in. diam wire. Wire Drawing—Tungsten carbide dies were used for the AT-400 and 1100 F alloys. They had an included angle of about 15 deg and reduced the wire area approximately 7 pct per pass. Steel dies with an included angle of 11 to 13 deg and an average reduction per pass of 10 pct were used for drawing the MD 2100 alloy, because drawing this alloy through the carbide dies produced overdrawing defects. Heat Treatment—The cold-drawn wires were cut into small samples, and the deformed ends were etched off. The samples were each wrapped tightly in a single layer of aluminum foil, and individually isothermally annealed in a lead bath. Metallography—The modes and kinetics of recrystallization were determined by metallography. Mounted and polished specimens were anodized in a solution of 1.8 pct HBF4;4 examination under polarized light clearly revealed their grain structures. The recrystallized grains were generally much larger than those of the unrecrystallized matrix, and could clearly be distinguished because they alternated between maximum and minimum light reflection when the microscope stage was rotated, while the unrecrystallized matrix had a comparatively homogeneous "salt and pepper" structure. The fractional recrystallized volumes of the dispersion hardened alloy wires were determined by cutting and weighing of recrystallized and total transverse areas on photomicrographs. The recrystallized grains in the 1100 F alloy were too small to be cut out individually; therefore a combination of cutting and lineal analysis was used in this case. RESULTS AND DISCUSSION Modes of Recrystallization—The modes of recrystallization of the three alloys varied widely. In the 1100 F alloy nucleation and growth started in the region midway between the center and the surface;

Jan 1, 1961

By J. Chipman

There is no better way of paying tribute to the memory of a scientist than by developing and carrying forward those ideas which he has contributed to science and which are for us the very essence of his immortality. For a lecturer who has not had the great privilege of stdying under Professor Howe or &apos;ven of knowing him in person, these ideas must be transmitted through the printed word. It is our great good fortune that Professor Howe left to us a rich heritage of publication, not only in his classic monograph on the "Metallography of Steel and Cast Iron" but in a wealth of earlier hooks and papers in the transactions of this Institute arid of other scientific and engineering bodies. An outstanding characteristic of this published record is the great breadth of interest and of vision which it portrays. His was riot a narrow specialization in only the scientific aspects of ferrous metallographg. On the contra1y many of his important contributions had to do with a far broader field of metallurgicial endeavor. He insisted that his students be well grounded in 1 he fundamentals underlying the whole field and not led into the narrow groove of specific applications. Among his first major publications we find papers on copper smelting, extraction of nickel, the efficiency of fans and blowers, thermic curves of blast furnaces, the cost, of coke, and the manufacture of steel. These are the papers of a metalhurgical engineer and it was among engineers that Henry Marion Howe made his early and well-merited reputation. These early engineering contributions display very clearly the strongly sctientific inclination of their author. The classic work on "The Metallurgy of Steel" published in 1890 contains a thorough and critical discussion of all that was known at the time concerning the alloys of iron and of what we would now call the physical metallurgy of steel. In addition it describes steel-making processes in use and some that had become obsolete, and points out in critical fashion the reasons for success and failure. Steel mill design and layout were included as well as some pertinent discussion of refractories. The book is indeed an embodiment of one of Howe&apos;s outstanding characteristics—breadth. It is both the science and the engineering of steel production as known in that day. One of Howe&apos;s earliest technical papers was entitled "What is Steel?" That was nearly seventy-five years ago when many new processes and new kinds of steel were being developed. The time was ripe for such a question and the answers which Howe was able to give were helpful in understanding the phenomena of heat treatment. Twenty-five years ago Professor Sauveur repeated the question as the title of the first Henry Marion Howe Memorial Lecture. It seemed to him that this question, "What is Steel?," had served as Howe&apos;s motto throughout the remainder of his life. Today I shall present for your consideration a question of another sort: "What is Sletallurgy?" Perhaps it is not too much to hope that in the answer we may obtain a clearer and possibly broader view of the nature of our science and our profession. The time is ripe for giving careful consideration to what we mean by metallurgy. If our Metals Branch is to become in fact an American institute of Metallurgical Engineers, it is essential that we understand what is meant by metallurgical engineering. I am convinced that the best interests of the profession have not been served by a narrow interpretation of these terms. We must now place emphasis on the breadth of metallurgy as a science and as an engineering profession. With its usual brevity and wit. Webster&apos;s dictionary definesmetallurgy as "the science and art of extracting metals from their ores, refining them and preparing them for use." I shall riot assume that the words "science" and "art" and "metal" are so well understood as to require no defining but others among our contemporaries are better qualified than either your lecturer or the dictionary to present the broad meanings of these terms. When we say that metallurgy is among the oldest of the arts we are not classing it with painting or sculpture or music but rather with the making of tools or weapons or the building of bridges or chariots or cathedrals. In short we are saying that metallurgy is among the oldest of the engineering professions. The question " What is metallurg ? " has been one of rather more than ordinary concern to those of us who have the task of developing a curriculum for the education of students in this field. This development has been going on in a number of universities over a period of some years. but there seems to be as yet no unanimity as to what such a curriculum should contain. I believe there is fairly complete agreement that it must be founded upon sound

Jan 1, 1950

By H. Conrad, V. V. Damiano, G. J. London

A method is described for producing single crystals of high-purity beryllium, Be-4.37pct Cu, and Be-5.24 pct Ni. These crystals were prepared for testing in compression parallel to the [0001] by orienting and lapping to within ±3&apos; of arc of the (0001). Microstrain testing apparatus is described along with c axis compression results for ingot purity beryllium, twelve-zone-pass material, and the above-mentioned alloys. Results show no measurable plasticity for the ingot purity material from -196" to 400°C, although some surface traces of (1122) slip was observed at 200°C and above. The twelve-zone-pass material shows substantial microstrain plasticity at 220°C with slip on (1122). Both alloys show significant plasticity at room temperature and above with slip also on (1122) planes. THE two slip systems which normally operate during the plastic deformation of beryllium in the vicinity of room temperature are:&apos; basal slip (0001)(1120) and prism slip . Pyramidal slip with a vector inclined to the basal plane has been reported for elevated temperatures,&apos;-a but occurs near room temperature only at very high stresses.~ A summary of the available data on the effect of temperature on the critical resolved shear stress for slip on these systems has been compiled by Conrad and Perlmutter.~ It has been postulated6&apos;7 that one of the principal factors contributing to the brittleness of poly crystalline beryllium at temperatures below about 200°C is the difficulty of operating pyramidal slip with a vector inclined to the basal plane. Hence, detailed information on the operation of such a slip system is important to understanding the brittleness of beryllium. The operation of pyramidal slip with a vector inclined to the basal plane is best accomplished in beryllium by compressing single crystals in a direction parallel to the c axis. In such a test the resolved macroscopic shear strzss on the basal and prism planes is zero and (1012) twinning which is favored by tension along the c axis does not occur. Hence, in c axis compression of beryllium the normal deformation modes are inhibited and the operation of pyramidal slip with a vector inclined to the basal plane is favored. In the present investigation, c axis compression tests were performed on beryllium single crystal as a function of temperature (77" to 700°K), purity (commercial and twelve zone pass), and alloy content (4.37 wt pct Cu and 5.24 wt pct Ni). Presented here is a description of the test techniques employed and the gross mechanical behavior observed. A detailed analysis of the slip traces developed on the surfaces of the deformed specimens during these tests and the results of electron transmission studies of the deformed crystals are given in a separate paper.B PROCEDURE 1) Materials and Preparation. Single crystals about 1 in. diam were prepared of the following materials: commercial-purity beryllium, high-purity beryllium, and two beryllium alloys, one with 4.37 wt pct Cu and the other with 5.24 wt pct Ni. The commercial-purity single crystals were obtained by cutting specimens from large-grained ingot of Pechiney SR material, which is approximately 99.98 pct pure. The high-purity crystals were prepared by floating-zone refining (twelve passes) a rod (7 in. by 1 in, diam) of Pechiney SR grade cast and extruded beryllium. Although an absolute chemical analysis of the zone-refined material was not established, mass spectro-graphic analysis, emission spectrographic analysis, and y activation analysis indicated that it contained in atomic fractions about 5 to 10 ppm each of carbon and oxygen, 1 to 5 ppm each of nickel and iron, and about 1 to 2 ppm of copper, with the remaining residual impurities being less than 1 ppm. Further indication of the purity of this material is provided by the critical resolved shear stress for basal slip, which was approximately 300 psi. The starting material for the alloy single crystals was 1-in.-diam floating-zone-refined (six passes) rod of Pechiney SR grade beryllium. Two such rods were wrapped respectively with sufficient weight of wire of high-purity copper (99.999 pct) or nickel (99.999 pct) to yield a 5 wt pct alloy. A seventh floating-zone pass was then applied to each of the rods to accomplish the initial alloying and an eighth pass for homogenization. Analytical samples were taken from regions of the rod immediately adjacent to where the mechanical test specimens were cut; these indicated 4.37 wt pct Cu and 5.24 wt pct Ni. 2) Crystal Orientation. To avoid the occurrence of basal slip during c axis compression testing, it is necessary to load the crystals as nearly parallel to the c axis as possible. Preliminary c axis compression tests indicated that plastic flow and/or fracture occurred at stresses of the order of 300,000 psi; hence on the basis of a critical resolved shear stress for basal slip of 300 to 400 psi, the maximum crystal misorientation permitted is about 4 to 5&apos; of arc. Since this accuracy cannot be obtained using the usual back-

Jan 1, 1969

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2&apos;3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By R. A. Burmeister, G. P. Pighini, P. E. Greene

An open tube vapor phase epitaxial growth system has been used for large area (multiple substrate) growth of GaAs1-xPx on GaAs substrates. The GaCl-GaCl transport reaction is used with either a GaAs or Ga (nonsaturated) source. Selenium and tellurium have been used for donor impurities, and zinc as an acceptor. The useable substrate area in this system is approximately 20 sq cm. The uniformity of thick-ness of the epitaxial layers are typically better than ±5 pct across a given wafer. Electrical and optical measurerments indicute comparable uniformity in electrical and luminescent properties within a wufer. The application of this system to the large scale pro-duction of GaAs1-x Px for display devices, both discrete and arrays, is discussed. Typical electrical and luminescent properties of light emitting diodes fabricated front material produced by this technique are presented. THE most promising materials currently being utilized for visible injection electroluminescence are GaAs1-xPx, Ga1-xAlxAs, and Gap. All have reasonably efficient emissions in the red portion of the visible spectrum at room temperature; Gap also has an efficient green emission.&apos; At present, GaAs1-xPx has a technological advantage over Ga1-xAlxAs and Gap for display applications, since relatively large (several sq cm) areas of GaAs1-xPx suitable for use in electroluminescent devices may be readily grown by vapor phase growth techniques. In contrast, the preparation of Gap and Ga1-xAlxAs for electroluminescent device applications generally employs solution growth techniques which are at present not well suited for the growth of large areas of uniform thickness and doping level. The capability of uniform growth over large substrate areas and the use of multiple substrates is necessary for the practical utilization of electroluminescent devices. This is particularly important when quantity production or monolithic devices are required. Furthermore, in many display applications arrays of light emitting devices are used, the individual elements of which are of a size resolvable by the unaided eye. Thus the overall dimensions of display are substantially larger than those of most semiconductor devices. It is also necessary to achieve a high degree of control over the growth parameters to attain the required degree of reproducibility of materials properties for electroluminescent devices. In the case of GaAs1-xPx it is necessary to accurately and precisely control the phosphorus content of the alloy, both on a macroscopic and microscopic scale, in addition to the parameters generally associated with epitaxial growth such as thickness and doping level. This value is critical, as it has a major effect on the performance of electroluminescent devices. This paper describes the epitaxial growth of GaAsl-xPx suitable for electroluminescent display devices using a system developed specifically for this purpose, and which contains several novel features. The results of studies of selected physical properties of the epitaxial layers are also discussed. Finally, a brief summary is given of the characteristics of display devices fabricated from GaAsl-xPx grown in this system. EXPERIMENTAL A) Reactants. A number of techniques suitable for the vapor phase epitaxial growth of GaAs1-xPx have been reported in the literature.&apos;-&apos; The method selected for this investigation is that in which the Ga is transported by the GaC1-GaCI3 reaction in an open tube process. The results reported here were obtained using either the combination of GaAs, AsC13, and pH3, or Ga, AsH3, pH3, and HC1 as the initial re-actants.* The ASH3 and pH3 were obtained as dilute *Several different sources of supply were used for these reactants, y~elding comparable results._____________________________________________________ mixtures in HZ; the HC1 was obtained from the reduction of AsC13 by Hz at elevated temperatures. Both selenium and tellurium were employed as donor impurities, and zinc as an acceptor impurity. Selenium was introduced in the form of H2Se, tellurium in the form of tellurium-doped GaAs, and zinc in the form of diethy1 zinc. B) Apparatus. The prinicipal difference between the apparatus used in the present study and that of Tietjen and Amick,8 in addition to size and other related design features, is that RE induction heating is utilized in place of resistance heated furnaces. Induction heating was selected for this application because it appears to have several advantages, including: 1) It is possible to keep all fused silica portions of the apparatus at temperatures well below those of the reaction zone, thus minimizing a possible source of contamination. 2) The thermal mass of an induction heated system can be made small, thus reducing the total time required for the growth process. 3) Sharp temperature profiles (desirable for high deposition efficiency) are easily achieved. 4) The volume of the system for a given substrate area can generally be made smaller than a comparable resistance heated unit. This results in shorter time

Jan 1, 1970

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330&apos; ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti&apos; indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

By A. J. Shaler, H. Udin, J. Wulff

In the study of the sintering of meta powders, we have come to the conclusion in this laboratory that further progress requires a more basic understanding of the operating mechanisms. This is emphasized in detail by Shaler. He has shown that a knowledge of the exact value of the surface tension is imperative for a solution of the kinetics of sintering. This force plays a principal role in causing the density of compacts to increase.2 Furthermore, a knowledge of the surface tension of solids is also applicable to other aspects of physical metallurgy. C. S. Smith3 points out the relation between surface and interfacial tension and their function in determining the microstructure and resulting properties of polycrystal-line and polyphase alloys. This paper describes one group of results of an experimental program designed for the study of the surface tension in solid metals. As a by-product of this work, considerable information has been obtained on the rate and nature of the flow of a metal at temperatures approaching the melting point and under extremely low stresses, a field of mechanical behavior heretofore scarcely touched by metallurgists. The importance of this additional information to students of powder metallurgy need not be stressed. Theoretical Considerations Interfacial tension arises from the condition that an excess of energy exists at the interface between two phases. Gibbs proves that this energy is a partial function of the interfacial area; thus: ?F/?s = ? where ?F/?s is the rate of change of free energy of the system with changing surface area, at constant temperature, pressure and composition, and ? is the interfacial tension, or interfacial free energy per unit area. If one of the phases is the pure liquid or solid, and the other the vapor of the substance, ? may properly be termed "surface tension," and is a characteristic of the solid or liquid. The attempt of a body to lower its free energy by decreasing its surface gives rise to a force in the surface which is numerically equal in terms of unit length to the free energy per unit area of the surface. Thus ? may be expressed either in erg-cm-² or in dyne-cm-1. Similarly, surface tension may be determined either by a thermo-dynamic measurement of the surface energy or by a mechanical measurement of the surface force. We have chosen the latter approach. Tammann and Boehme4 determined the surface tension of gold by measuring the amount of shrinkage or extension of thin weighted foil at various temperatures and interpolating to zero strain. The method is of questionable accuracy because of the tendency of foil to form minute tears when heated under tension. Their assumption of F = 2W?, where W is the width of the foil, is unsound, as the foil can decrease its surface area by transverse as well as by longitudinal shrinkage. Although their experimentation was meticulous, the paper does not include details of the sample configuration required for recalculating ? on a correct basis, even if such a calculation were possible. In the experimental procedure chosen here, a series of small weights of increasing magnitude are suspended from a series of line copper wires of uniform cross-section. This array is brought to a temperature at which creep is appreciable under extremely small stress. If the weight overbalances the contracting force of surface tension, the wire stretches; otherwise, it shrinks. The magnitude of the strain is determined by the amount of unbalance, so a plot of strain vs. load should cross the zero strain axis at w = F?. If balance is visualized as a thermodynamic equilibrium, the critical load is readily calculated. At constant temperature, an infinitesimal change in surface energy should be equal to the work done on or by the weight: ds = wdl [A] For a cylinder, s = 2pr2 + 2prl [2] If the volume remains constant, r = vV/pl [31 s = 2vpl+2V/l [4] ds = vpv/l - 2V/l²) dl [5] Substituting [5] into [I] gives for the equilibrium load, w = ?(z/rV- 2V/12) [6] and, again expressing V in terms of r and l, w = pr?(1 - 2r/l [7] Here the end-effect term, 2r/l, is neglected for thin wires in subsequent work. Eq 7 can be confirmed by means of a stress analysis. If the x-axis is chosen along the wire, then the stress is 2pr? - w pr² pr2 [8] A cylinder of diameter dis equivalent to a sphere of radius r, insofar as radial surface tension effects are concerned.³ Thus xv = 2?/d = ?/r = sz [9] For the case of zero strain in the x direction, the strain will also be zero in the y and z directions. Since the wire is under hydrostatic stress, Eq 8 and 9 are

Jan 1, 1950