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By W. M. Raynor

LARGE quantities of "midnight oil" have been consumed by researchers in attempting to develop a process to produce cold ductile zirconium at low cost. The tantalizing facts that zirconium is a bright, silvery, tarnish-proof metal and is 2 1/2 times as abundant in the earth's crust as copper, and thirteen times as plentiful as lead have resulted in much speculation on uses, ranging from automobile radiator grills to kitchen sinks. but unfortunately no low-cost process of producing it has so far been found. In the case of zirconium, we cannot say that "virtue is its own reward" for the principal virtues of the metal, namely, corrosion resistance at ordinary temperatures and ability to absorb gases at high temperature, are the very characteristics that defeat all of the usual recovery methods such as sintering, plating, or direct chemical reduction. The only method giving a pure metal sufficiently low in oxides, nitrides, etc. to be truly cold-malleable is the one developed by Van Arkel and DeBoer in 1925. This process involves decomposition of zirconium tetraiodide in contact with a hot filament and pre

Jan 1, 1947

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By P. S. Kotval, O. H. Nestor

Stacking fault energy measurements of nickel-base alloys have been mainly confined to binary and ternary systems. In this paper, the stacking fault energy has been measured by the rolling texture method in a series of ten alloys which comprise successive additions of Cr, Mo, Fe, and C to pure nickel, eventually resulting in an alloy of the composition of Hastelloy alloy X. The alloys studied here are single-phase, solid solutions with the exception of two alloys in which some undissolved particles of "primary" carbide have been retained. It is found that successive additions of chromium, molybdenum, and iron all lower the stacking fault energy, with iron having only a minor effect. The stacking fault energy is found to increase when carbon is added in solid solution. The results from the rolling texture measurements are correlated with thin foil observations of dislocation substructures in these alloys. In a recent paper' it was pointed out that the dislocation substructure of various superalloy matrices could be classified into three broad categories based on 'high', 'medium', and 'low' stacking fault energy. It has also been demonstrated2 that the dislocation substructure in each of these categories has a well defined role in the nucleation of strengthening precipitates which is different from the role played by the dislocation substructure in other categories. Thus, it becomes desirable to understand the influence of various solute elements on the stacking fault energy and hence on the dislocation substructure of the matrix, before any further development of superalloys by mi-crostructural predesign can be undertaken. Recently, Beeston and France have studied the influence of increasing solute additions on the stacking fault energy of a series of binary nickel-base alloys relevant to the Nimonic series using the rolling texture method, and have then estimated the effect of a given alloy addition in five commercial Nimonic alloys. However, comparison with stacking fault energy data from other investigations''5 suggests that the influence of a given solute element in a nickel-base binary system is not necessarily the same in a ternary or more complex superalloy system. Accordingly, the present work was undertaken to study the effect of successive addition of solute elements to pure nickel, the final composition being the nominal composition of Hastelloy X. The rolling texture method of stacking fault energy measurement was used since it can be used for the whole range of stacking fault energy values and does not have the disadvantage of, say, the Node method which is only applicable to low values of stacking fault energy. In addition, the rolling texture method provides a means of determining the stacking fault energy which is statistically more significant than that provided by other methods. EXPERIMENTAL TECHNIQUES Button heats of alloys of the compositions shown in Table I were prepared. Each button was remelted not less than four times. After a slight deformation (approximately 5 pct) all alloys were homogenized at 2200°F except alloys, H . I, and J. Alloys H and I were solution heat treated at 2150°F and alloy J at 2282OF. The buttons were cold worked by rolling, using "end-to-end" passes and intermediate anneals at the homogenization temperatures mentioned above. After each annealing treatment the samples were rapidly water quenched to avoid any precipitation. In alloys F and I, however, a few particles of "primary" carbides were retained even after the homogenization treatments at the temperatures mentioned above. Part of the solution heat treated material was cold worked to 0.04-in.-thick sheet and the penultimate reduction was -50 pct of deformation as recommended by Dillamore et al. All annealing was carried out in vacuo within sealed quartz capsules. Some of the material from each alloy was rolled down further to 0.004 in. strip for thin foil transmission electron microscopy specimens. Specimens of this strip were annealed at the homogenization temperature for 1 hr and then strained 7 pct by rolling at room temperature. Thin foils were prepared from the strip specimens by the 'window" technique using an Ethanol-Perchloric acid electrolyte at 32°F and a voltage of 22 v. Stainless steel cathodes were employed. All transmission electron microscopy was performed in a JEM-7 electron microscope using an accelerating voltage of 100 kv. Specimens from the 0.04 in. sheet which had been rolled -60 pct in the final pass were electropolished to remove the surface layers to a depth of approximately 0.002 in. Rolling texture pole figures for all the alloys were determined using a Schulz ring and nickel filtered CuKa radiation at 50 kv and 20 ma. The texture parameter Io/(lo + I,,) (where Io is the

Jan 1, 1970

By P. C. J. Gallagher

A number of recmt determinations for the ratio of extrinsic to intrinsic stacking fault energy in fcc solid solutions are examined. Some of these arise from incomplete analyses which can yield only approxi?nate values for the ratio. Reliable results, on the other hand, obtained using extrinsic-intrinsic fault pairs, show that the extrinsic and intrinsic fault energies are essentially equal in several materials. There is some reason to believe that this finding is of general applicability to fcc elements and alloys. A wide range of values has been obtained for the relative magnitudes of the extrinsic and intrinsic stacking fault energies (yext and yint, respectively) in recently published studies in a variety of materials. In contrast, Hirth and Lothe' using a central force model have shown that out to tenth nearest-neighbor interactions the perturbation in energy caused by both types of fault is the same. Although the model used is not completely valid in metals, there is nevertheless some indication that marked variations of yext/nnt should not be observed from one material to another. In early work in Cu-A1, Cu-Ge, Ni-Co, and stainless steel all the deformation faults observed in the electron microscope were found to be intrinsic in nature, which led to an attitude that the extrinsic fault energy must be considerably greater than the intrinsic. Extrinsic faulting arising from deformation has, however, more recently been directly observed in Au-4.8 at. pct n;~ Ag-6 at. pct Sn and Ag-8 at. pct sn; Ag-7.5 at. pct In and Ag-11.8 at. pct 1n;"' pure silwer and Ag-0.5 at. pct ~n;' and Cu-22 at. pct Zn, Cu-30 at. pct Zn, and Cu-7.5 at. pct ~1.l' Multilayer loops containing extrinsic faulting have also been observed in quenched aluminum." While peak asymmetries in X-ray faulting probability studies were generally attributed to the presence of twins,Lelel2 has recently reinterpreted earlier X-ray data in Ag-Sb alloysU in terms of the presence of extrinsic faulting. The determinations of yeXt/yint made from the above studies are shown in Table I, with a brief description of the techniques employed. A number of the methods utilized are deficient in one or more respects, and the reliability of the values listed will be discussed. ~ele'~ recognizes that his approximate determinations of yext/yint assumes equal numbers of extrin-sically and intrinsically faulted dislocations. It is well-known, however, that such an assumption is not at all justified since extrinsic faulting has but rarely been observed in samples studied in the electron microscope. The only conclusion that should be drawn from the X-ray results at present is that the total intrinsic scattering cross section (i.e., the product of the width of the intrinsically faulted dislocations with their density) is approximately ten times greater than for extrinsic faulting in these particular samples. An important point is that the relative magnitudes of the energies cannot be inferred from results of this type, unless the intrinsic and extrinsic faults form with equal ease. One must recognize that, although a formation barrier may restrict the amount of extrinsic faulting which occurs, this in no way implies that the extrinsic and intrinsic energies should be different. It is unlikely that a worthwhile estimate of the relative densities of extrinsically and intrinsically faulted dislocations can be made at the high deformations present in X-ray samples. ~oretto,'~ from a statistical argument applied to the nonobservation of extrinsically faulted tetrahedra out of a large sample, concluded that yeXt/yint could not be less than -4.5. However, the present author feels that a high-energy formation barrier as just supposed also explains this finding satisfactorily and that no conclusion can possibly be drawn concerning the actual extrinsic stacking fault energy. The same argument also serves to explain the fact that extrinsic faulting has been relatively little observed in the electron microscope. Extrinsic-intrinsic node pairs and isolated extrinsic nodes were first reported by Loretto~ and subsequently by Ives and Ruff,' Gallaher,' and Gallagher and Wash-burn.' Ives and Ruff' found a wide spread in the ratio of extrinsically to intrinsically faulted area in the node pairs they observed, and drew the very tentative conclusion that yeXt/yint 2 2. They recognized that a straightforward comparison of the size of the faulted areas could provide no more than a qualitative result without a theoretical analysis of the dislocation geometry associated with extrinsic faulting. A theoretical

Jan 1, 1969

By P. H. Lindon, J. C. Billington

Fe-O melts containing 0.045 pct 0 were deoxidized with Mn-Si-A1 alloys. Product compositions were reluted to the melt and alloy compositions and were found to be most sensitive to the aluminum content of the alloy. Low residual oxygen contents could be obtained when aluminum oxide was present in the Products because of the reduction of silica and manganese oxide activities. Flotation of the Products from a quiescent melt was followed both by analysis of the oxygen content and metallographic measurement of inclusion concentration. MnO-SiO2-A12O3 products were found to float most rapidly when their composition was such that their viscosity may be expected to be low. Changes in the particle size distribution indicates that particle coalescence occurred and differences in the degree of coalescence are thought to be responsible for the different flotation rates observed between products 0f differing composition. Measured flotation rates were slower than those Predicted from a model based on Stoke's Law, although alumina flotation might be reasonably accounted for by this model. Interfacial effects between oxide particles and the melt are believed to be responsible for the discrepancy. It has been recognized that deoxidation products constitute a large proportion of the nonmetallic inclusions present in killed steel. The amount of oxide inclusions which originate as deoxidation products depends largely upon three factors. These may be summarized, according to P16ckinger1 as: 1) Amount of primary products remaining in the steel prior to cooling. 2) Residual dissolved oxygen content of the steel after deoxidation. 3) Amount of secondary products, formed during cooling and solidification, which remain entrapped in the solid steel. In a well-deoxidized steel containing residual aluminum and/or silicon, the equilibrium dissolved oxygen content is usually very low and so the maximum amount of oxide which may be produced as secondary deoxidation products is small in comparison with the amount of primary products. It may be seen, therefore, that the amount of indigenous nonmetallic inclusions may be minimized if a low dissolved oxygen content is achieved by deoxidation and if the primary deoxidation products are efficiently removed. Oxides which originate by reaction of the metal stream with the atmosphere during teeming are not considered in the present study. It is known that two or more deoxidizers may result in a lower equilibrium oxygen content when used in conjunction with one another than when any of the individual deoxidizers are used alone. Equilibrium studies by Hilty and crafts2 and by Bell3 have shown that manganese increases the effectiveness of silicon as a deoxidizer, and Walsh and Ramachandran4 relate this to a reduction in the activity of silica in the products as the manganese :silicon ratio in the steel increases. It was also shown by Herty's work on deoxidation of steel by silico manganese alloys,5 that there existed an optimum ratio of manganese to silicon which gave a minimum inclusion content. This ratio was in the range 4:l to 7:l and the (FeO-MnO-SiO2) products formed by such deoxidation practice were found to lie in a composition range having very low liquidus temperatures (1170 to 1250°C approx). The optimum manganese:silicon ratio was then explained by postulating that these fluid products were able to coalesce and that the larger particles formed floated out of the steel very quickly as predicted by Stoke's Law. The present work examines the effectiveness of various Mn-Si-A1 alloys as deoxidizers and their effects on the composition and removal of primary deoxidation products from a quiescent melt. EXPERIMENTAL TECHNIQUE Approximately 250 g of prepared Fe-O alloy, containing 0.045 to 0.055 pct O, were melted in an alumina crucible and deoxidized at 1550°C by plunging a thin steel cartridge containing the deoxidizer below the melt surface. A high frequency induction furnace supplying current at 8.5 kHz was used to heat a graphite susceptor, the interior of which had been machined to give a wall thickness of 0.85 in. to form a receptacle for the alumina crucible. The iron melt was essentially quiescent as the induced current was concentrated at the external surface of the graphite susceptor by the skin effect. A nonoxidizing atmosphere was maintained over the melt by passing a continuous stream of argon through the lid of the susceptor. The melt temperature was measured before deoxidation, and again at the end of an experiment by means

Jan 1, 1970

By V. B. Kurfman

The temperature, strain rate, and orientation deDendence of defbrnzation of single-crystal MgAg has been examined. The crystals exhibit a tendency to single glide and little or no hardening at 25°C for many orientations. A much higher hardening rate is observed when multiple glide occurs, such as can be initiated by surface defects. The tendency for easy glide becomes less dependent on surface preparation and orientation as T — 100°C and bars so tested often fail after one-dimensional necking-. At T > 200°C (transition temperature for single-crystal notch sensitivity and poly crystalline ductility) single glide diminishes and two-dirnensionul necking begins. The crystals do not strictly obey a critical resolved shear stress law, but show the influence of {loo) cracks in determining the slip mode. The results are correlated with the difficulty of sciperdzslocation intersection and semibrittle behavior of this compound in single-crystal and poly crystalline form. Comparisons are made with the slip selection mode observed in tungsten, with the reported observations of easy glide in bee metals. and with the mechanical behavior of poly crystalline MgAg. PREVIOUS work on tensile deformation of polycrys-talline MgAgl and bending deformation of single-crystal MgAg2 has shown that the compound is semi-brittle (i.e., notch and grain boundary brittle). If this semibrittleness is supposed to result from the difficulty of multiple glide (associated with the problems of superdislocation intersection) one might expect single crystals deformed in tension to show pronounced single glide and strong orientation dependence of hardening rate. These experiments were done to examine this supposition and to study the tensile deformation of a highly ordered system which may be considered bcc if the difference between the two kinds of atoms is ignored (actual structure: CsC1). EXPERIMENTAL Single-crystal ingots were grown by directional freezing as previously described.' These ingots were sliced into a by a by 2 in, rectangular bars by electric discharge machining, then round tensile bars were conventionally machined to 1/8-in.-diam by 1-in.-long reduced section. The bars were typically tested without an anneal because of the problem of magnesium vapor loss and they were typically tested as mechanically polished. The analyses are within the same limits as those reported earlier; i.e., the average composition for each specimen is within 0.5 at. pct of stoichiometry, while the total range from end to end in a given specimen varies from 0.7 to 1.4 at, pct. There has been no indication in the results of any variation in slip or fracture mode attributable to the composition fluctuations. The slip systems were determined by two-surface analysis of the bars after testing to failure at room temperature. Single glide was so dominant that there was little difficulty in identification of the dominant slip system even though the tensile elongation to failure often approached 7 to 8 pct in room-tempera- ture tests. Elevated-temperature testing was done in a silicone oil bath and low-temperature testing was done in liquid Np or a dry-ice bath. All stress measurements are reported as engineering stress unless otherwise specified, and crosshead travel is used as the strain measurement. RESULTS The tendency toward single glide is best seen in the pictures, Figs. 1, 2, and 3, which depict deformation at fracture as a function of test temperature. While it is possible to find regions of secondary slip by careful microscopy, such regions are very small. The development of a ribbon-shaped configuration from an initially round section bar pulled at 100°C is typical, occurred by single glide, and illustrates the degree to which such glide continues. At temperatures =100°C the bars typically show elongation of 20 to 50 pct by predominently single glide. Despite the large elongation, fracture even at 150°C occurs in a brittle mode, Fig. 2, in the sense that it is an abrupt failure which shows no discernible necking in the second dimension of the bar's cross section (i.e., there is no appreciable action of any slip modes which would decrease the broad dimension of the cross section). Near 200°C the fracture mode changes slightly. Although most of the sample extension is by single glide, after the bar develops the characteristic ribbon shape it begins to neck in the second (i.e., broad) cross-sectional dimension. The bar becomes very thin in the "necked down" region, Fig. 3, and the reduction in area approaches 100 pct. Often there oc-

Jan 1, 1967

By S. G. Cupschalk, J. J. Wert, R. A. Buchanan

The uniaxial deformation of thermally ordered and disordered polycrystalline Cu3Pt was studied by means of the X-ray line - broadening analysis according to Warren and Averbach and the extension of this analysis to ordered fcc materials by Mikkola and Cohen. Because of the heat treatment history, extinction had a pronounced effect on the X-ray spectra of ordered and disordered C%Pt at small plastic strains. After an appropriate correction for extinction, the long-range order in thermally ordered ChPt was found to decrease at a slow constant rate with plastic strain. Furthermore, the antiphase domain probability increased at a constant rate to 17.5 pct strain. The effective particle size behavior indicated that the stacking fault energy is lower in ordered than in disordered Cu3Pt. Analysis of the stress-strain curves shouled that ordered Cuzt has a slightly lower yield Point but a much higher work-hardening rate than disordered Cu3Pt. THE presence of long-range order in a solid-solution alloy has a marked effect on its mechanical properties. While this effect has been known qualitatively for many years, it was not until recently that detailed investigations have been performed to determine the exact role long-range order plays in this strengthening mechanism. The development of an advanced, quantitative. X-ray diffraction analysis by Warren and Averbachl and the extension of this analysis to the L1, type super lattice by Mikkola and cohen2 have greatly accelerated research in this field. The research reported in this paper consisted of two primary phases. The first phase was to determine the effect of long-range order on the tensile properties of polycrystalline Cu3Pt. This objective was accomplished by comparing the stress-strain behavior of thermally ordered CusPt to that of thermally disordered CusPt. The second phase of the research was to determine the difference between the atomic arrangements in thermally ordered and thermally disordered Cu3Pt as a function of uniaxial deformation and thereby gain a deeper insight into the mechanism by which long-range order affects the tensile properties. This second objective was accomplished by applying the Warren-Averbach method of peak profile analysis to the X-ray diffraction patterns obtained from ordered and disordered Cu3Pt after given amounts of uniaxial deformation. EXPERIMENTAL PROCEDURE The Cu3Pt was prepared by vacuum melting and casting. After a homogenization anneal, the ingot was cold-rolled to sheet form. Two tensile specimens with gage sections of 2.50 by 0.500 by 0.115 in. were carefully machined from the sheet. The specimens were polished with a final step of 600-grit paper to insure smooth diffracting surfaces. Finally, one specimen was heat-treated to yield an average grain diameter of 0.016 mm and an initial degree of long-range order, S, of 0.825. The other specimen was water-quenched from above the critical temperature, 645"C, to yield an average grain diameter of 0.017 mm and zero long-range order. The heat treatment history of each specimen is shown in Table I. The tensile tests were performed utilizing a Research Incorporated Model 900.95 Materials Testing System. This unit employs a closed-loop feedback system which maintains a constant strain rate through an extensometer clipped to the gage section of the tensile specimen. A strain rate of 1.32 i0.02 x 10"4 sec-' was employed in testing both specimens. In the X-ray diffraction analysis, a General Electric XRD-5 diffractometer equipped with a pulse-height analyzer set for 90 pct efficiency was employed. The goniometer speed selected was 0.2 deg, 20, per min. Filtered Cu radiation was used for all peaks and all peaks were chart-recorded. Because of nonuni-form grain size. it was necessary to spin the specimens during X-ray analysis in order to obtain reproducible integrated intensities. The spinning rate was 2000 i100 rpm. The application of the Warren-Averbach method of peak broadening analysis to a diffraction pattern is very time consuming if done manually. In this research, the calculations involved were performed with the aid of a computer program by wagner.3 As reported by Wagner, the program is written in Fortran TV computer language. It was modified to Fortran I1 so as to be handled by the IBM 7072 computer at Van-derbilt University. In the X-ray diffraction analysis of uniaxially deformed Cu3Pt, the 100, 200. 400. 111, and 222 reflections were recorded from the initially ordered sample after 'plastic strains of 3.0, 6.0, 9.0, 12.0,

Jan 1, 1970

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)' molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),' which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.' This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

In 1936 the Institute established the Anthony F. Lucas Gold Medal, which will be awarded from time to time "for distinguished achievement in improving' the technique and practice of finding and producing petroleum." These awards will be sponsored by the Petroleum Division. Captain Lucas was a pioneer in the oil industry, one of the early wildcatters and a leading mining and petroleum engineer. He was famous as the discoverer of Spindletop. He became a member of the Institute in 1895 and in 1913 was the first Chairman of the Petroleum and Gas Committee of the Institute, the forerunner of the present Petroleum Division. He also headed the Committee in 1914, 1917 and 1918. Medals Awarded To J. Edgar Pew, February, 1937 Henry L. Doherty, February, 1938 Committee on Award H. H. Power, Chairman Until Feb., 1939 Until Feb., 1940 R. Ogarrio W. B. Heroy H. H. Power C. V. Millikan Carl A. Young J. Edgar Pew Until Feb., 1941 Until Feb., 1942 Joseph Jensen M. Albertson John M. Lovejoy H. L. Doherty Carroll H. Wegemann E. G. Gaylord Members ex-officio D. C. Barton John W. Finch Axtell J. Byles D. C. Jackling

Jan 1, 1938

By F. P. Dewey

(Read at Amenia Meeting, October, 1877.) AT the Wilkes-Barre Meeting of the Institute, Dr. J. Lawrence Smith, in the course of his remarks on some peculiarities in the composition of irons, alluded to the so-called " buckshot" iron, and exhibited a specimen of this material. He said that when the small granules, or shot, were separated from the mass, they could be flattened under the hammer, and inferred that these particles had been decarburized by the blast before sinking into the hearth of the furnace, and thus we had the exceptional production of wrought iron in the blast furnace. I have recently obtained a characteristic specimen of this variety of iron from one of the furnaces at Orbisona, Pa. Considerable uncertainty existed as to its true nature and the conditions of its production. Its weight seemed to preclude the idea that it contained much or any slag, yet its lack of strength indicated that it was not homogeneous cast iron. At times considerable quantities had been produced, which could only be utilized by charging in the furnace and remelting. The specimen, on the freshly fractured surface, appeared to consist of flattened globules of iron cemented together by a bluish material which one would naturally suppose to be slag, and qualitative examination for lime strengthened this supposition. It was quite difficult to obtain drillings, as there was a tendency to split in several directions as soon as pressure was applied ; but enough was obtained to undertake quantitative determinations. They were found to consist of two portions-one attracted by the magnet, and the other not. By repeated separation the magnetic portion was found to be 94.44 per cent., and the non-magnetic 5.56 per cent. Analyses of these gave the following results :

Jan 1, 1878

By Mark C. Malamphy

During colonial times, Brazil was famous for the richness of her alluvial gold deposits. Paul Ferrand has estimated that the gold produced during the period from 1700 to 1820 was the equivalent of some 64 million pounds sterling. Since that time, most of the more prolific alluvial deposits have been exhausted. A few gold mines are still functioning, notably the Morro Velho mine, which is one of the deepest mines in the world. Today, the gold production of Brazil is insignificant when compared with world figures, but there are still many gold-bearing regions and it is probable that in at least some of them profitable returns would result from an exploitation program taking advantage of all the most modern innovations in gold mining and ore treatment on a large scale. In order to demonstrate the value of some of these abandoned prospects and stir up interest in increasing the national gold production, the government has stimulated research. Experimental plants have been and are being established in various places, and tests on large quantities of ores are being carried out on a semicommercial basis. The Geological Survey of the State of Minas Geraes is very active in this line and the Federal Institution is also showing an increased interest in the matter. One of the lesser known gold-bearing regions of Brazil is in the vicinity of Lavras, in the State of Rio Grande do Sul. Gold was first reported from this region in the early part of the nineteenth century. In 1811, D. João VI sent an experienced prospector from Minas Geraes to investigate the validity of the reports. According to the reports of Baron Eschwege, he succeeded in extracting some 30,000 Oitavos (about 105 kg.) during the first few years, but the production costs exceeded the value of the gold obtained.

Jan 1, 1934

By J. Szekely

The paper discusses simultaneous heat conduction and diffusion. These problems may arise in slag-metal kinetics and in connection with rapid heating or cooling of specimens. A mathematical formulation is given and it is shown that the transients due to either the variability of the diffusion coefficient with temperature, or thermal diffusion, are unlikely to be important for molten or solid metals and slags. The negligibility of these effects is due to the large values of the ratio thermal diffu-sivity/molecular diffusivity. In many problems relating to transport-controlled metallurgical kinetics the diffusion process is accompanied by the transfer of heat; large-scale metal refining or metal reduction may be quoted as examples. It has been shown that due to turbulent mixing in these systems the relevant transport phe- nomena are best described in terms of "surface renewal models" which require the solution of the unsteady-state diffusion equation.1-1 Problems involving simultaneous diffusion and heat conduction are also encountered in the laboratory in connection with rapid heating or cooling of specimens. The effect of variable temperature on diffusion may be twofold: a) in the absence of "cross effects" the problem, due to variable temperature, is that of diffusion with a variable diffusion coefficient; b) if the Soret Effect is nonzero, thermal diffusion must also be taken into account in the formulation. Although information is available on thermal-diffusion transients in a steady-temperature gradient,4'5 little work has been done on the effect of unsteady temperatures on either the diffusion coefficient or on thermal diffusion.' In the following a formulation is given and solutions presented with a view of examining the areas where these effects may be important.

Jan 1, 1965

By H. H. Stoek

Danville, the county seat of Montour county, Pa., was one of the earliest and best-known centers of the iron intlustry in the State. It is situated on the north bank of the north branch of the Sosquehanna river, twelve miles east of the confluence of the north and west branches of that river at Northurnberlttnd. The ore-belt, extending for a distance of twelve miles along the north bank, has been developed in a number of places, but nowhere so extensively as in the immediate vicinity of Danville. Hence, a description of the mines in that locality will suffice, as typical of the workings of the entire section. Geology. The Montour ridge consists of an anticlinal fold extending from the source of Wapwollopen creek on the east to the west branch of the Susquehanna, which it reaches at the mouth of Chilisquaque creek. According to the reports of the First Geological Survey of Pennsylvania, the length of the ridge is nearly twenty-seven miles, with an average breadth of three-fourths of a mile, and a maximum elevation of six hundred feet in the vicinity of Danville, where it also attains its greatest width. Just north of Danville the Mahoning creek cuts through it, exposing the iron-ore on the hill-side, where advantage has been taken of this to work the beds on the southern slope of the ridge by means of drifts. The sections given in Fig. 1 are taken from the reports of the First Geological Survey of Pennsylvania, made in 1858, by H. D Rogers, whose description of the Moatour ridge was so complete and accurate that the entire report was reprinted as an appendix to Vol. G 7 of the Second Geological Survey. The approximate crosssection shows that near Danville the top of the ridge is of Clinton vol, xx.—24

Jan 1, 1892

ABIDE from the John Fritz Medal, in which the Institute participates through its representation on the John Fritz Medal Board, the Institute itself has three major awards to make annually and one special prize for excellence in technical papers, as follows. The Robert W. Hunt Medal and Prize, The J. E. Johnson, Jr., Award, the James Douglas Medal, and The Lewisohn Platinum Prize to senior members. ROBERT W. HUNT MEDAL AND PRIZE The partners of Robert W. Hunt established a fund which was presented to the Institute at a fitting' ceremony on May 27, 1920, to establish an annual medal and a sum of money to be awarded under the following rules ? 1 The award shall consist of two prizes, first of a gold medal, second of a sum of money, a certificate to accompany each prize. The money prize shall not be awarded to a member over 40 years of age, but under unusual circumstances, both prizes may be allotted to one person provided that he is not over 40 years of age In general it will be understood that the Committee shall award the money prize to the younger men, rather than the medal. 2 The awards shall be made not oftener than once a year to that person or persons contributing to the Institute the best original paper or papers on iron and steel The scope of the term "iron and steel" shall be determined by the sub-committee considering the awards In general, papers dealing with the practical side of the subject have preference over those dealing with the theoretical side in recognition of the fact that Captain Hunt's main contributions to the industry have been in the improvement of production and quality of material

Jan 1, 1923

The Institute is one of the five national societies that joined in organizing the Congress, the others being the American Society of Civil Engineers, the American Society of Mechanical Engineers, the American Institute of Electrical Engineers, and the Society of Naval Architects and Marine Engineers. Each society has pledged from its general funds or some special fund a certain sum to guarantee the success of the Congress. To this the engineers resident on the Pacific Coast added $13,000, the total guarantee fund amounting to $37,000. It is hoped that this money, iii part or in whole, can be repaid to the guarantors of the Congress. The sums necessary to conduct the latter and to publish the proceedings, are to be derived from membership fees paid equally by all participating. A member of the Institute as such is not a member of the Congress and will not receive any of the publications of the latter. He is eligible to become a member of the Congress and it is hoped that he will do so. The membership fee is $5, and this entitles one to receive the introductory volume of the Congress containing the proceedings; a digest of the other volumes and a general index. It also entitles the member to one other volume of the transactions, to be chosen as he will. For moderate sums he can buy additional volumes, the whole set costing delivered, $30 or less. On Jan. 12 the total membership was 2,350, of which only 290 were recorded as mining engineers. Full details regarding the Congress have been sent to every member of the Institute, and the failure of the members to take a more active interest in the matter is believed to be due to some misunderstanding of the situation.

Jan 4, 1915

By T. M. Williams

DURING the year just ended we have had three great fires in the mines in the Wilkes-Barre district. One at the Empire Colliery, one at the Prospect shaft, and the other at the Baltimore old mine. It is proposed in this paper to give a brief history of the fire at the Empire Colliery, and the methods employed in extinguishing it. The fire was first discovered breaking out in the air-stack, alongside what is known as the " Kidder Plane," about one o'clock on the morning of December 31st, 1873. Subsequently it was ascertained that the fire originated in the return airway somewhere near the steam boiler, located inside the mine, near the head of No. 5 slope. The coal from this slope was hoisted to the shaft gangway, at a point nearly four thousand feet distant from the foot of the shaft. As there were from four to five hundred mine cars hoisted per day from this slope the steam boilers were located at this place. The mines being of considerable extent required a large volume of pure air for ventilation, and no fan having been erected at this slope at the time, the heat from the boiler was made use of to assist ventilation, by conveying the return air from No. 5 slope into the large airway made from these boilers to the surface through the old "Kidder slope" to the stack where the fire was first discovered. The length of this slope or airway was about one thousand feet, with a sectional area of about sixty feet. The quantity of air passing through it must have been over sixty thousand cubic feet per minute

Jan 1, 1875

By Joseph Pogue

IT IS well known that one of the cornerstones of economic theory is the so-called law of supply and demand, which, really, is a group of economic laws, one of which may be succinctly stated : A rise in price tends, sooner or later, to increase supply. It is the fear that, in the case of petroleum, a limited natural resource, a point will soon be reached when supply will not respond adequately to price advances, which in recent years has prompted a movement for oil conservation. This movement has lately taken concrete shape in the appointment of a Federal Oil Conservation Board by the President. An important aspect of the law of supply and demand is that the supply of any commodity is not an entity per se, but is a factor of price. Supply, without the specification of price, has no exact meaning; and in practice supply cannot be divorced from considerations of price. Mathematically, supply may be expressed by the formula SP, which means that supply varies with price, just as the value of 10 raised to the x power varies with x. In its technical usage, supply is the quantity of a commodity that is bought currently on the market at a given price. In the case of a natural resource, however, this quantity will eventually depend not alone on price but on the physical volume of the reserve that exists and. that, in consequence, can respond to the stimulus of price. If this reserve is fixed in size, we must sooner or later reach a point where supply can no longer respond to price in the usual degree and a permanent shortage. will develop which no advance in price can correct, except in so far as higher prices may curtail demand or improve the efficiency of utilization.

Jan 3, 1925

By J. C. Jaeger

It frequently happens in engineering and mining situations that "bad" rock is encountered which consists of rock broken up into blocks a few inches or less in diameter by a network of intersecting joints. These joints may be open, or filled by veins of solid material, or covered with weathering products. Essentially, the material consists of an aggregate of small interlocking blocks. In such circumstances, major joint systems usually can be recognised and studied, but there are probably many minor planes of weakness which may cause the blocks to be of almost random shape. It is extremely difficult to determine the properties of such materials. Measurements on small specimens give the properties of the constituent rock and not the jointed material. At the other extreme, the material has occasionally been tested as loose aggregate in large triaxial pots, but this gives no information about the strengthening effect of the interlocking of the small blocks of rock. One simple approach, which has been much used, is to regard the rock as randomly jointed on a small scale and to apply soil mechanics theory to it. In this case, the normal and shear stress at failure are related by [ ] where the coefficient of friction p and the cohesion c will be those of the individual joints. Even in very bad rock, it is usually possible to drill core in small diameters of 1 to 2 in. which will contain a number of joints, both open and filled. The testing of such joints provides one simple method of determining some of the properties of closely jointed rock and will be discussed in detail in the next section. Calculations based on Eg. 1 with values of c and µ obtained in this way may be expected to give a lower limit for the strength of structures in rock.

Jan 1, 1970

By J. F. Kemp

IN submitting an additional contribution to the discussion on ore-deposits in the recent volumes of the Transactions, it is my desire to adhere closely to matters of material importance as affecting the actual processes. Judging from the discussion by Professor Van Hise, and from one or two reviews or other articles by associates of his in geological work, the impression seems to prevail that, in so far as my paper* referred to ,his masterly essay,†I was guilty of misconceptions regarding both the part attributed by him in it to the igneous rocks and the ubiquitous presence of the ground-water. I should regret extremely to be wanting in these particulars or to have misunderstood one for whose great services in this and other branches of geology no one has a higher esteem than myself. I have, however, in the most careful way, and with these points in mind, read his essay again, anti, taking it as a whole, I cannot gain any different impression of relative magnitudes than the one first received. The importance of the igneous phenomena and the restrictive influence of the processes described by " cementation " in their effect upon the ground-water, as set forth in Professor Van Hise's " Discussion " (Trans., xxxi., 292), impress me as being in very marked contrast with the same things in his first essay. If the point seems to anyone of sufficient importance, it can easily be decided by reading the originals. My paper was the result of some years of observation, reading and reflection, and was meant to be an independent contribution, controversial only in some subordinate particulars. In depicting the drama of the deposition of ores, I cannot but feel that Professor Van Rise assigned to the chorus and the scene-shifters some characters which, it seems to me, should

Jan 1, 1913

By R. L. Wilcox, M. L. Fuller

Owing to the nature of the die-casting process, fresllly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effeet of reaching a state of equilibrium at the aging temperature, beyond which no fnrther change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (I) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time. Scope of Study In the present investigation a special technic for the study of the beta phase in zinc-alloy die castings has been developed, making possible the determination of the period of existence of the beta phase after casting. The pure beta constituent and its decomposition have been studied in detail. The effect of magnesium and copper on the velocity of the decomposition is reported. The heat of decomposition, the eutectoid temperature arid the accompanying density change have been measured. The density change lias been calculated from data on crystal structure and the result thus obtained has been compared with the actual change.

Jan 1, 1935