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By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By T. D. Murphy, G. V. Henderson

The element silicon, with its usual partner, oxygen, plays the same role relative to inorganic materials as carbon and hydrogen play with respect to living organisms. The crystallographic structure of silicon dioxide (SiO2) consists of one atom of silicon well-nigh inseparably bonded to four contiguous atoms of oxygen, a gas of but slightly more than half its atomic weight, forming a three-dimensional network of SiO4 tetrahedra (Dietz, 1968). This wispy arrangement is the fabric of the mineral quartz which is one of the harder, more abrasive, and chemically stable raw materials to be found in Mother Nature's cupboard. Most of us are vaguely familiar with the observation that nearly 60% of the lithosphere to an approximate depth of 10 miles is composed of these two elements, which proportion actually rises to about 75% if the atmosphere, hydrosphere, and biosphere are included (Parker, 1967). Elemental silicon is a brittle steel-gray metalloid with a density of 2.42 and does not occur in nature. In its limited commercial form, which is still brittle and metallic in appearance, its density drops to 2.33. It combines with oxygen to form the gaseous oxide SiO, or the solid dioxide Si02 (analogous to its congener carbon in CO and CO2); a tetrachloride SiCI4 (analogous to CC14); or, combining with oxygen and one or more metal ions, forms the largest rock-making family of all, the silicates. Further, next to the feldspars, quartz is the most abundant known mineral and, in some form or another, accounts for roughly 12% of surficial terrestrial rock. It is this so-called "free silica" to which your attention is chiefly directed in this chapter. In any such consideration of silica, its several crystalline phases with their attendant differing physical properties appear worthy of delineation. Alpha quartz is the only one of this interesting polymorphic family that is thermodynamically stable at normal pressures and temperatures up to about 573°C. The low phases of tridymite and cristobalite can exist in the so-called metastable state below 117° to 200ºC but seldom occur in nature in these two different crystal forms (Sosman, 1965). Opaline silica, now considered by most researchers to be a variety of cristobalite, occurs in abundance and is the only exception. The three remaining polymorphs, keatite, coesite, and stishovite, also are metastable under ambient conditions. Keatite, however, is not known to occur naturally and has only been synthesized in the laboratory. The other two have been identified in submicron sizes and in microscopic amounts, occurring naturally as a result of high order shock-wave pressures generating quite elevated temperatures --such as might accompany the impact of a large meteorite on a hard sandstone terrain (Chao et al., 1962). An intriguing characteristic of these silica minerals, and one which has very practical applications, is their extremely variable densities. The classic 2.65 specific gravity of alpha quartz drops to 2.20 in tridymite, cristobalite, and lechatelierite (natural silica glass), as well as in many man-made glasses of commerce which are merely noncrystalline or amorphous solids in the form of super-cooled liquids which can no longer change their shapes (Pauling, 1950). It rises again to 2.50 and 2.93 for keatite and coesite, respectively, and finally becomes a reported 4.35 for stishovite-nearly a 50% range in density for the known physical combinations that silica naturally assumes (Frondel, 1962; Konnert et al., 1973; Pecora, 1960). Pursuing its esthetic aspects, briefly, silica is well-represented among gem stones which, to qualify as such, must have the attributes of beauty, durability, and rarity (Jahns, 1983). As quartzose gems usually have but one or, at

Jan 1, 1983

By John W. Weeton, Max Quatinetz, Robert J. Schafer

Nickel powders of 1-, 0.4-, and 0.2- average particle size were combined with 0.05- p MgO powder. Oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were vacuum hot pressed and extruded at 2100°F. In spite of a general tendency to growth of oxide particles during processing, dispersions of fineness comparable to those of Sintered Aluminum Powder, SAP, were achieved. A small amount of oxide considerably improved 1800°F stress-rupture strength, but further oxide addition resulted in a decrease of strength. RECENTLY there has been much speculation concerning the requisites for strong and stable dispersion-strengthened alloys. The nature of the dispersed phase, the stability of the alloys, and variables influencing the mechanical properties of alloys have been given consideration. Such topics have been reviewed by Bunshah and Goetzel. Of the many parameters related to the mechanical properties of dispersion alloys, mean free path between dispersed particles (a measure of the fineness of the dispersion), particle size, and vol pct of the dispersed phase have been shown to be very important. Generally, strength increases with decreasing mean free path, and there is an optimum vol pct of dispersed phase. Just how fine a dispersion ought to be is somewhat open to debate, but Irmann, Lenel, Backensto, and Rose, Gregory and Grant,4 and others have shown in the original SAP-type alloys, aluminum plus aluminum oxide alloys, that better strength is generally obtained with finer dispersions and the best strengths were obtained when the mean free path was less than . Further, Cremens, and rant' showed that in nickel plus aluminum oxide alloys, stress-rupture strength at 1500°F was definitely increasing with decreasing mean free path. In their investigation, however, the finest dispersions that were produced were about 2.0 mean free path. To determine the potential of the nickel plus oxide type of product, it would be neces- sary to obtain dispersions analogous to those of SAP alloys; namely, ones where the mean free path between oxides is less than . Unfortunately, however, it is very difficult to produce extremely fine dispersions of oxides in metals other than those which naturally form refractory oxide skins. There are several approaches to this problem including such procedures as mechanical mixing, internal oxidation, reduction of mixed oxides, and metal deposition from solution. Work at the Lewis Research Center has shown that metal powders 0.1p or finer could be produced by ball milling, when selected grinding aids were utilized.' Because these unusually fine powders were available, it was an initial objective of this study to determine if by mixing of these fine Ni powders with various amounts of MgO (0.05) a fine dispersion of MgO in Ni comparable to those in Al-Al203 might be achieved. A second objective was then to attempt to relate the parameters of structure to 1800°F stress-rupture strength of the alloys. Nickel powders of 1-, 0.4-, and 0.2-p average particle size were combined with 0.05- average particle size MgO powder. This oxide was added in quantities of 4, 12, and 20 vol pct. The mixtures were hot pressed and extruded at 2100°F.

Jan 1, 1962

By R. I. Jaffee, J. G. Dunleavy, W. Hodge, H. R. Ogden

IN a search for an improved conductor for use in field wire for the L. S. Army Signal Corps, an alloy of copper and silver was developed from which it was possible to obtain 29 B & S ga. strands with tensile strengths in excess of 160,000 psi combined with an electrical conductivity of over 70 pct IACS. Such a favorable combination of strength and electrical conductivity has not been reported previously in the rather extensive literature covering this subject. The properties obtained from various binary alloys of copper and silver, together with the method of fabrication of these alloys which has been developed to obtain the properties desired in fine wire strands, are discussed in this paper. LITERATURE The effect on the electrical conductivity of copper of the various elements in solid solution is shown in Fig I, taken from published data by J. O. Linde and others.' It will be noted that silver in solid solution depresses the electrical conductivity to a lesser extent than any other element for which data are given, and is followed rather closely by cadmium, and then by chromium. Zinc, which lies between cadmium and chromium, has so high a solid solubility in copper that the data for zinc are scarcely comparable to the data for the other two in the range covered. Not many data are available on the strain hardening of copper-rich Cu-Ag alloys. Corson2 reports a 3 pct Ag alloy properly cold worked and annealed to have 100,000 psi tensile strength and 90 pct IACS conductivity. On straight cold working, Hessenbruch3 reports 101.000 psi for a 5 pct Ag, 0.3 pct Be alloy, and 129,000 psi for a 30 pct Ag, 0.5 pct Be alloy. Here it would he expected that much of the strain hardening came from the silver content of the alloys. The copper-rich side of the Cu-Ag diagram, according to Stockdale,4 is shown in the upper part of Fig 2. The electrical conductivities for copper-silver alloys annealed at 750 and 350°C, taken from the work of Johansson and Linde,5 are shown in the lower part of Fig 2. The sloping line corresponds to the conductivity of solid solutions of silver in copper, and the horizontal offshoots correspond to the conductivity of the two-phase alloys in equilibrium at the two temperatures shown. The electrical conductivities are very high, even for the 750°C anneal. The potentiality for age hardening from supersaturated alpha copper solutions appears to be excellent from the solubility line, but Smith and Lindlief6 have shown that the response to age hardening of solution-annealed alpha alloys is not good. They found that the tensile strength of a 5 pct Ag alloy aged at various temperatures was not as great as in the quenched condition, even though, anomalously, the hardness increased from RB68 to RB78 by annealing for 4 hr at 400°C after a 750°C quench. Weist7 also found that the alloys increased in hardness

Jan 1, 1948

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.' Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.' STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By A. E. Worthington, R. F. Meldau

An analog computer study was made of the reduction of the magnitude of the SP by formation geometry and resistivity effects. Practical field .situations were studied. The analog data were converted to the form of departure charts. These charts may he used to determine the reduction in the SP due to the above eflects pith good precision Quantitative interpretation of the SP log in terms of formation water resistivity is presently based on the premise that the observed SP is equal to the electrochemical potential developed across a shale between the mud filtrate and the formation water. This procedure inherently assumes that, first, no electro kinetic (streaming) potential is present, and, second, that the SP is not reduced by resistivity or geometry effects in the formation. When, however, such a reduction of the observed SP does occur, one may write, SP = b,E, b, E, (1) where SP is the observed self-potential opposite the center of the bed under consideration. In this case, E, is the electrochemical potential, E, is the electrokinetic potential, b, is the electrochemical reduction factor, and h, is the electrokinetic reduction factor. The first assumption above is equivalent to assuming E, = O in Eq. 1 and the second assumption is equivalent to h, = b, = 1. Examination of electric logs shows that for many formations of interest the observed SP is reduced below its maximum value. The object of this work is to aid quantitative SP interpretation in at least some of these situations by obtaining values for b, and b, in Eq. 1 as functions of realistic combinations of bed thickness, depth of invasion, and formation resistivity. The only previously published work in this field known to the authors is by H. G. Doll' in 1948. He evaluated b, under conditions permitting exact analytical solution. His work clearly established the importance and qualitative nature of formation geometry and resistivity effects upon the SP, but the necessity of obtaining analytical solutions restricted his study to situations of limited practical interest. In order to extend such studies to practical combinations of formation parameters which do not lend themselves to feasible analytical solutions, the results reported in this paper were obtained by use of a special analog computer. THE ANALOG MODEL The analog model used for this study was the Guyed Analog Computer which originally was designed and built for resistivity log departure curve studies. It consists of a two-dimensional mesh of resistors, with the vertical mesh corresponding linearly to vertical distance along the borehole, and the horizontal mesh corresponding to radial distance from the borehole axis. By proper choice of horizontal resistor values, a three-dimensional, axially symmetric, borehole-formation problem can be modeled with this two-dimensional array. These and other details of the model are contained in a paper by H. Guyod'. The geometry used for the SP studies with the analog is depicted in Fig. 1. This configuration has a horizontal plane of symmetry, and, hence, the model, and the following discussion, need only to be concerned with one quadrant such as shown in Fig. 2. A further simplification arises by considering that both the natural potential sources and those used in the model have fixed internal impedance. Therefore, the current flows produced by these sources can be separated and studied independently ( i.e., the superposition theorem can be applied). SP = SP, i SP, = h,E, + b,E, ,(7)

By H. R. Thresh

An oscillational vis cometer has been constructed to measure the viscosity of liquid metals and alloys to 800°C. An enclosed cylindrical interface surrounds the molten sample avoiding the free surface condition found in many previous measurements. Standardization of the apparatus with mercury has verified the use of Roscoe's formula in the calculation of the viscosity. Operation of the apparatus at higher temperatures was also checked using molten lead. Extensive measurements on five different samples of zinc, of not less than 99.99 pct purity, indicate i) impurities at this level do not influence the viscosity and ii) the apparatus is capable of giving reproducible data. The variation of the viscosity ? with absolute temperature T is adequately expressed by Andrade's exponential relationship ?V1/3 = AeC/VT , where A and C are constants and V is the specific volume of the liquid. The values of A and C are given as 2.485 x 10-3 and 20.78, 2.444 x 10-3 and 88.79, and 2.169 x 10-3 and 239.8, respectively, for mercury, lead, and zinc. The error of measurement is assessed to be about 1 pct. Prefreezing phenomena in the vicinity of the freezing point of the zinc samples were found to be absent. AS part of an over-all program of research on various phases of melting and casting nonferrous alloys, a systematic study of some physical properties of liquid metals and their alloys was undertaken in the laboratories of the Physical Metallurgy Division.1,2,3 The most recent phase of this work, on zinc and some zinc-base alloys, was carried out in cooperation with the Canadian Zinc and Lead Research Committee and the International Lead-Zinc Research Organization. One of the properties investigated was viscosity and the present paper gives results on pure zinc; the second part, on the viscosity of some zinc alloys, will be reported separately. Experimental interest in the viscosity of liquid metals has virtually been confined to the past 40 years. The capillary technique was already established as the primary method for the viscosity of fluids in the vicinity of room temperature; all relevant experimental corrections were known and an absolute accuracy of 1 to 2 pct was possible. Ap- plication of the capillary method to liquid metals creates a number of exacting requirements to manipulate a smooth flow of highly reactive liquid through a fine-bore tube. Consequently, the degree of precision usually achieved in the high-temperature field rarely compares with measurements on aqueous fluids near room temperature. However, the full potential of the capillary method has yet to be explored using modern experimental techniques. As an alternative, many investigators in this field have preferred to select the oscillational method. Unfortunately, the practical advantages are somewhat offset by the inability of the hydrodynamic theory to realize a rational working formula for the calculation of the viscosity. In attempting to overcome this restriction many investigators have employed calibrational procedures, even to the extent of selecting an arbitrary formula for use with a given shaped interface. However, where calibration cannot be founded on well-established techniques, the contribution of such experiments to the general field of viscometry is questionable. A critical appraisal of the viscosity data existing for pure liquid metals reveals a somewhat discordant situation where considerable effort is still required to establish reproducible and reliable values for the low-melting point metals. The means of rectifying this situation have gradually evolved in recent years. Here, the theory of the oscillational method has undergone major advances for both the spherical and cylindrical interfaces. The basic concepts of verschaffelt4 governing the oscillation of a solid sphere in an infinite liquid have been adequately expressed by Andrade and his coworkers.5,6 Employing a hollow spherical container and a formula, which had been extensively verified by experiments on water, absolute measurements on the liquid alkali metals were obtained. The extension of this approach to the more common liquid metals has been demonstrated by culpin7 and Rothwel18 where much ingenuity was used to surmount the problem of loading the sample into the delicate sphere. Because of the elegant technique required to construct a hollow sphere, the cylindrical interface holds recognition as virtually the ideal shape. On the other hand, loss of symmetry in one plane increases the complexity of deriving a calculation of the viscosity. The contributions of Hopkins and Toye9 and Roscoe10 have markedly improved the potential use of the cylindrical interface in liquid-metal viscometry. The relatively simple experi-

Jan 1, 1965

By C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970

By Don B. Shupe, John K. Berry

The handling and disposal of mine water is a much larger problem than is apparent at first glance. Many more tons of water are removed from underground coal mines in the United States each year than tons of coal. In the old anthracite region of Pennsylvania the average was around 32.7 t (36 st) of water for each ton of coal produced, while bituminous mines average about 4.5 or 5.4 t (5 or 6 st). Water encountered in the mines may come from several different sources. In mines with light cover and without a firm solid roof, rain may seep directly into the workings. This is also true of deeper mines where pillar falls have broken the roof to the surface. The top under creek beds is generally faulty and broken and water comes through the roof at this point. Deeper mines are frequently overlain by water-bearing strata and pillar breaks and faulty top can admit water, while places running to the dip often accumulate water which comes up through the bottom. In all cases, except where passing under a year-round stream, the amount of water made is usually pretty closely connected with the weather-more water during the rainy season, less in the dry, although the deeper a mine is, the longer it is before changes in rainfall are felt. Another source of water, not connected with seasonal changes, is old water, accumulated over a period of time in abandoned workings of the mine, or from flooded adjacent mines. Here the water filters through the coal, the parting, or comes up through cracks in the bottom. Similarly, core holes, drilled to prospect the property, can be a source of unexpected water and modern safety requirements for dust-allaying water at the working faces can turn a pleasant working area into a soggy mess over the weekend if the system is not properly maintained and operated. Why water must be disposed of is obvious. If allowed to accumulate, sooner or later the mine will fill up, or at least it will become "roofed" in low places, blocking ventilation and traffic. It must be controlled long before it reaches this stage. Water standing in the working faces is

Jan 1, 1981

By S. N. Singh, M. C. Flemings

Results are presented of a detailed study on the combined influences of ingot dendrite am spacing and thermomechanical treatments on the structure and solution kinetics of high --purity cast and worked 7075 alloy. Solution kinetics were found to depend sensitively on ingot dendrite am spacing and on details of therrnomechanical processing, including amount of reduction and extent of&apos; solution treatment before reduction. An approximate analysis is given for rate of solution of nonequilibrium second phase in the cast and worked structres; results of the analysis are compared with experiment. MICROSEGREGATION in high strength aluminum alloys manifests itself as "coring" (composition differences within the primary aluminum-rich phase), and as interdendritic second phase. The mechanism of formation of the microsegregation is understood, and approximate prediction of the amount of second phase is possible for simple binary systems.1,2 When alloy elements or impurities are present in amounts less than their solid solubility at solution temperature, any phases forming from these elements are termed "nonequilibrium" and can be dissolved by appropriate solution treatment. The rate at which the nonequilibrium phases are removed depends sensitively on their spacing (dendrite arm spacing in the cast material, or band spacing in wrought material). When alloy elements or impurities are present in amounts in excess of their solubility at the solution temperature, second phase particles form an "equilibrium" second phase that does not dissolve in heat treatment and may, in fact, coarsen in such treatment. Usual commercial, high strength, wrought aluminum alloys contain nonequilibrium second phases that were not fully dissolved during ingot processing. They also contain equilibrium second phases resulting from impurities present in amounts greater than their solubility. As has been shown by Antes, Lipson, and Rosenthal,3 and will be demonstrated further in a subsequent paper by the authors,4 significant improvements in mechanical properties of high strength alloys can be achieved by reduction or elimination of these second phases. Methods of elimination are 1) to employ high purity materials to minimize amounts of equilibrium second phase, and 2) to employ suitable thermomechanical processing techniques to fully eliminate nonequilibrium second phases. Work reported herein comprises a study of selected thermomechani- cal processing treatments, and of their influence on solution kinetics of wrought high purity 7075 alloy. EXPERIMENTAL PROCEDURE Melting and Casting. The bulk of the work reported was performed on a single ingot of high purity 7075 alloy. The ingot was 4 in. by 4 in. by 8 in. high, uni-directionally solidified following a procedure previously described.5 The mold was heated to 1350°F before pouring the melt. The bottom chill was carbon coated stainless steel. Water was circulated through the chill after the melt was poured. The 7075 alloy was prepared from high purity virgin material (aluminum, zinc, magnesium) and from master alloys (Al-50 pct Cu, A1-15 pct Cr, A1-5 pct Ti). Final measured melt composition (wt pct) was: Zn Mg Cu Cr Ti Fe Si Al 5.70 2.28 1.35 0.18 0.15 <0.002 <0.012 bal Melting was done in a silicon carbide crucible; all tools were coated with zircon wash to minimize iron contamination; degassing was by bubbling chlorine through the melt. che-rmomechanical Treatments. Detailed studies were made on material taken from a location approximately 13 in. from the chill and 51/2 in. from the chill (i.e., from 1 in. thick slices taken between 1 and 2 in. from the chill and between 5 and 6 in. from the chill). Solution treatment was done at 860°F in an air-circulating furnace with a "bottom drop" arrangement to achieve minimum delay time between solution treatment and quench. Samples solution treated in this way were 2 in. by 2 in. by 1 in. Temperature of the quench water was approximately 10°C. Mechanical reduction was by cold rolling. Samples 11/2 and 51/2 in. from the chill were treated for 12 and 24 hr, respectively, before cold rolling. Reduction by cold rolling was then 4/1, 16/1, and 35/1. In each case, several intermediate anneals (1/2 hr at 860°F) were used to permit reaching the final thickness without cracking; two such anneals were used for the 4/1 reduction, five for 16/1, and six for 35/1. After working, materials were again solution treated for various lengths of time from 0 to 48 hr and quenched in water. Structural Measurements. Secondary dendrite arm spacings were measured using procedures previously described.&apos; For each measurement reported, five photomicrographs were first made at X75. Measurements were made of dendrite arm spacings in at least 20 different grains (grain structure was equiaxed). Grain size measurements were made by running a number of random traverses across photomicrographs of the samples and obtaining the mean lineal intercept. Measurement of the volume percent of second phase and porosity was done by quantitative metallography. A two-dimensional systematic point count was used

Jan 1, 1970

By W. Ivanick, Frank W. Glaser

ORDERING reactions of Fe-Si compositions in the a region have been mentioned in a number of review articles.7-8 However, little is known in regard to the critical temperature, T at which this transformation takes place. Greiner and Stoughton,&apos; in a study of the constitution of iron-rich Fe-Si alloys below 800°C, placed the onset of order at a composition of about 4 to 5 wt pct (7.5 to 9.5 atomic pct) Si. They observed that at this composition the ductility and strength begin to decrease sharply and brittleness develops. During X-ray studies they observed only the appearance of superlattice lines for compositions containing 12.5 atomic pct Si. More recent X-ray diffraction studies- etected the appearance of superstructure lines (corresponding to the calculated positions of [Ill] and [ZOO] reflections) for alloys containing 9.5 atomic pct. This fact confirms Greiner and Stoughton&apos;s original hypothesis in regard to the onset of order at compositions containing about 7.5 to 9.5 atomic pct Si. The physical properties.of Fe-Si alloys containing more than 10 atomic pct Si have been studied only to a limited extent. Their extreme brittleness and difficulties of sample preparation render them of little industrial use in comparison with alloys in the 0 to 10 atomic pct Si range. The properties of Fe-Si alloys reported to date are mostly properties measured at room temperature on ordered compositions It appears that because of experimental difficulties fully disordered alloys could not be produced in the critical composition ranges and their properties could therefore not be reported. In Figs. la, lb, and lc, a summary of physical properties of Fe-Si alloys, measured during recent investigations of the influence of silicon additions to iron, is presented. No mention of determination of the critical temperature, T for disorder could be found in the literature. The following is an account of work done in an attempt to: 1) produce the disordered state of various Fe-Si alloys and establish the critical temperature, T for disordering, and 2) compare the electrical and thermal conductivity characteristics of the ordered and disordered phases as functions of composition. Materials, Preparation of Test Samples, and Testing Methods Fe-Si alloys with high silicon contents (about 10 atomic pct) are usually prepared using powder metallurgy techniques. This method insures accurate compositions and high purity through the use of protective atmospheres during solid state diffusion alloying of the mixed powders."" Iron and silicon powders were mixed in the desired proportions, cold or hot pressed, and then homogenized at 1150°C for periods ranging from 6 to 12 hr under a protective getter and in a hydrogen atmosphere. Fully homogenized samples were quenched in water from various and successively higher temperatures to establish the critical temperature for disorder. Temperatures were determined using Pt—Pt-Rh thermocouples in contact with the test samples. Test bars were approximately 0.6x1.25x7.5 cm. Electrical measurements were made at room temperature by determining the potential drop over a 1.5 cm span for a current of 10 amp. Densities of the samples were determined by immersion. High temperature electrical resistivities were measured using previously described techniques.&apos;" Specific heat conductivity up to 200°C was measured by heating one end of the test bar and water-cooling the other; heat conductivity was then obtained by subtracting the rate at which heat entered the water from the

Jan 1, 1957

By D. V. Edmonds, C. J. Beevers

Tensile tests were carried out on a! titanium containing 850, 1250, and 2700 ppm 0, and up to -500 ppm H. The tests were performed at -196", -78", 20°, 150°, and 300°C at a strain rate of -1.0 x 10??3 sec-1. Increasing oxygen content, increasing grain size, and decreasing test temperature resulted in enhanced embrittlement of the a titanium by the hydrogen additions. Metallographic observations showed that this can be correlated with the influence of these parameters on the introduction of cracks into the a! titanium by fracture of titanium hydride precipitates. CRAIGHEAD et al.1 reported that the hydrogen content normally found in commercial-purity a! titanium (60 to 100 ppm) was sufficient to cause a substantial lowering of the impact strength, and they attributed this embrittling effect of hydrogen to the precipitation of titanium hydride. Lenning et al.&apos; found that in commercial-purity a titanium there is an almost complete loss of impact strength at about 200 pprn H, which is approximately half the value needed to eliminate the impact strength of high-purity a titanium. They also showed that the presence of 3000 ppm hydrogen reduces the room-temperature tensile ductility of commercial-purity material to a value of the order of 10 pct; the corresponding hydrogen concentration for high-purity titanium is over 9000 ppm. It thus appears that the detrimental effect of hydrogen on the mechanical properties of commercial-purity titanium becomes evident at much lower hydrogen contents than for high-purity titanium. The main difference between the two types of a titanium might be expected to be the higher level of interstitial impurity in the commercial-purity grade. Jaffee et a1.3 studied the influence of temperature and strain rate on the hydrogen embrittlement of high-purity and commercial-purity ! titanium. In general, the behavior was the same for both materials; embrittlement was enhanced by decreasing temperature and increasing strain rate. Recent results from tests on commercial-purity a titanium containing 850 ppm O and varying amounts of hydrogen up to -500 ppm showed that the degree of embrittlement by hydrogen is intimately related to the fracture characteristics of titanium hydride precipitates.4 The present paper considers the interrelationship between the mechanical properties and micro-structural features of commercial-purity a! titanium containing 850, 1250, and 2700 ppm 0 and varying amounts of hydrogen up to -500 ppm. 1. EXPERIMENTAL PROCEDURE Three types of commercial-purity titanium supplied by IMI* were used in the investigation, and for the *Address: Witton, Birmingham 6, United Kingdom. purpose of this paper are designated Ti 115, Ti 130, and Ti 160. The principal impurity elements are given in Table I. The material was received in the form of 12.7 mm diam bars having a fully recrystallized structure. Tensile specimens with a round cross-section of 4.5 mm diam and a gage length of 15.2 mm were machined from the bars. In order to develop the same grain size (mean linear intercept of grain boundaries) in each of the three types the specimens were annealed under a dynamic vacuum of <10?5 mm Hg, Table 11. Specimen hydriding was carried out in a modified Sieverts apparatus;&apos; hydrogen was taken into solution at 450°C and after holding the specimens at this temperature for 24 hr they were furnace-cooled to room temperature at an average rate of -100 C deg per hr. By this method nominal hydrogen contents of 0, 50, 100, 250, and 500 ppm were introduced into specimens of Ti 115, Ti 130, and Ti 160 (100 ppm (wt) -0.5 at. pct). The actual hydrogen contents were calculated from the weight differences obtained by weighing the specimens before and after the hydriding treatment. Tensile tests were carried out at temperatures of -196", -78", 20°, 150°, and 300°C on a 10,000 kg In-stron machine at a nominal strain rate of -1.0 x 10-3 sec-1. Fractured specimens were sectioned in planes parallel to the tensile axis, mechanically polished to 0.25 µm grade of diamond paste, and then attack polished using a solution containing by volume 99 parts H2O, 1 part HF, and 1 part HNO3. Although the latter treatment unavoidably opened out cracks and voids visible after mechanical polishing, it did reveal the grain structure, titanium hydride morphology, and deformation twinning structure.

Jan 1, 1970

By Morris Cohen, Robert C. Ruhl

Fe-Ni-B alloys were inresligated by X-ray diffraclion after splat quenching. Although this rapid cooling did not produce a measurable supersaturation of dissol1ed boron in either binary Fe-B or Ni-B alloys, a marked increase in dissolved boron was achieved by the splal quenching of lernary Fe-Ni-B alloys. Boron additions up to 2.0 wl pcl to Fe-13Ni and Fe-24Ni alloys cause an increase in retained austenite from 0 to 59 pet and to 92 pet, respectively. The martensitic phase in the Fe-13Ni-9 at. pct B alloy is .found to conlain about 0.6 at. pet interstitial boron, as evidenced by the tetragonality of this phase, and about 3.6 at. pct substilutional boron, us deduced from the lattice paratrieler decrease, the balance of the boron being precipitated as (Fe,Ni)aR. The austenitic Fe-Ni-B plznses also contain both interstitial and substitutional boron. Iron-Boron System. The phase diagram and related information about the solid solutions and intermediate phases in the Fe-B system are given by ansen,&apos; Elliott.2 and Pearson.1 The equilibrium solid solubility of boron in both ferrite and austenite is quite small: the maximum solid solubility of 0.02 wt pct B (0.11 at. pct B) occurs in iron at the eutectic temperature of 1150°C. while the maximum solubility in a iron is less than 0.01 wt pct.l There is disagreement in the literature as to whether these solid solutions are substitutional or interstitial. Based on the measured activation energy of boron diffusion in iron, it appears likely that boron moves interstitially in austenite. 4 However, this observation does not rule out the possibility that some of the dissolved boron may also occupy substitutional sites in this phase. Investigations of internal friction of boron in iron have suggested that boron is interstitial there.&apos; Shevelev, 5 on the other hand, reports a decrease in the ferrite lattice parameter with dissolved boron content, thus indicating a substitutional solution. Unfortunately. Shevelev&apos;s methods and analysis are unclear. Goldhoff and spretnak6 have measured the lattice parameters of pure iron and an Fe-0.005 wt pct B (0.027 at. pct) alloy at both room temperature (ferrite) and from 920° to 1200°C (austenite). They reporte: a lattice contraction in the ferrite of 0.0003 ± 0.0002 due to boron, thus indicating a predominately substitutional solution. Appreciable (0.0010 to 0.0060) lattice contractions were found in boron-containing austenites, but these effects were much larger than could be accounted for by the substitutional solution of all the boron present. Nickel-Boron System. Elliott 2 gives a summary of thephase diagram and recent work on this system. The solubility of boron in nickel reaches a maximum of 0.03 wt pct at the eutectic temperature of 1080°C. Iron-Nickel System. ansen&apos; presents the equilibrium diagram for this system and also discusses the metastable austenitic and martensitic phases along with the a=? transformations. The lattice parameters of Fe-Ni ferrites have been recently redetermined by Abrahamson and Lopata.7 Their data, Fig. 1, show an unusual change in slope at about 1.7 at. pct Ni. Very few measurements of the lattice parameters of Fe-Ni martensites are available in the literature. The values of Roberts and Owen8 are considerably higher than those measured in the course of the present work: they find that a, is constant at 2.874? from 8 to 30 at. pct Ni. Both the slope change in the ferrite parameters and the occurrence of a maximum plateau in the marten-sitic lattice parameters vs composition denote the

Jan 1, 1970

By G. Bhat, J. F. Libsch

lsoembrittlement curves depicting the influence of time and temperature in the range 800&apos; to 1260°F (425&apos; to 680°C) on the development of embrittlement in a commercial chromium alloy steel and a commercial molybdenum alloy steel are presented. Two distinct regions of embrittlement occur in the chromium alloy steel: I—at 800&apos; to 1000°F (425&apos; to 540°C) and 2—in the region just below the lower critical temperature. Embrittlement is most pronounced at 800&apos; to 1000°F, decreasing very rapidly with increasing temperature above this region, only to increase again as the lower critical temperature is approached. The data suggest two distinct modes of embrittlement with possible superposition of the two modes at extended embrittling times in the temperature range 1100° to 1150°F (590&apos; to 620°C). While the molybdenum alloy steel shows little susceptibility to embrittlement at 800&apos; to 1000°F (425&apos; to 540°C), considerable embrittlement may occur just below the lower critical temperature. THE subject of temper embrittlement in alloy steels has received considerable attention in the last few years. Points of view on the mechanism of embrittlement differ, however, resulting in part from the incompleteness of the data developed and in part from the speculation regarding the susceptibility of plain carbon steel to temper embrittlement. Libsch, Powers, and Bhat1 carried out short-time embrittling treatments on an AISI 1050 steel and demonstrated that hardened plain carbon steels are quite susceptible to embrittlement when tempered in the range from 850°F (455°C) to the lower critical temperature. The isoembrittlement diagram,&apos; representing the embrittling characteristics of this steel, is reproduced in Fig. 1. It is evident from the shape of the curves shown that embrittlement in plain carbon steel increases progressively with both temperature and time in the embrittling range. A comparison of the isoembrittlement diagram for AISI 1050 steel with that presented by Jaffe and Buffum&apos; for an SAE 3140 steel shows that up to 930°F (500°C) the isoembrittlement characteristics of the plain carbon steel are similar to those of SAE 3140 steel, although the embrittlement is much more severe in the latter steel. Above 930°F (500°C), the rate of embrittlement in the plain carbon steel increases continuously with increasing temperature; whereas, in the SAE 3140 steel, the embrittlement rapidly decreases. The influence of alloying elements upon embrittlement during tempering thus appears to cause a decrease in embrittlement above the region of maximum embrittlement, i.e., 850" to 1000°F. The question naturally arises as to what effect individual alloying elements have upon the embrittling characteristics of the plain carbon steel. Current knowledge on the influence of alloying elements on temper brittleness may be found in the review papers of Hollomon" and Woodfine. Hollo-mon," from the results of other investigators, has shown that, in general, the amount of embrittlement increases with increasing alloy content (except for molybdenum and possibly tungsten and columbium). Jaffe and Buffum," by a comparison of the embrittlement in a plain carbon steel with that of a SAE 3140 steel postulated that the presence of alloying elements in moderate amounts tends to retard the development of temper brittleness. It is difficult to determine what effect chromium has upon temper brittleness, since most of the information available has been based on the combined effect of other elements with chromium, particularly nickel and manganese. However, Wilten, and recently Jolivet and Vidal,&apos; Vida1, and Woodfine have reported that chromium steels are temper brittle, that the embrittlement is reversible with a maximum rate of embrittlement at approximately 975°F (525"C)," and that the susceptibility increases with increasing amounts of chromium. Taber, Thorlin, and Wallacel" have found a large embrittling effect with increasing chromium content in a medium C-Mn-Ni steel. But Hultgren and Chang," from their experiments conducted on synthetically prepared ternary Fe-C-Cr alloys, could not conclude that these alloys are susceptible to temper embrittlement. However, on addition of manganese or phosphorus, these Fe-C-Cr alloys became susceptible, from which fact they concluded that the embrittlement developed in chromium-bearing Fe-C alloys is due chiefly to the presence of these elements. Considerable data are available to show that molybdenum decreases the susceptibility of steel to temper embrittlement. However, its effectiveness in preventing or decreasing embrittlement appears limited to its presence in small amounts. Vidal" has shown that a plain 2 pct Mo steel was susceptible. Hultgren and Chang" also have shown that molybdenum additions in excess of 2 pct to synthetically prepared Ni-Cr steels did not prevent embrittlement. Jolivet and Vidal&apos; and Lea and Arnold found that molybdenum reduced temper brittleness. Lea and Arnold further stated that molybdenum decreased the rate of embrittlement rather than the total amount of embrittlement, whereas Preece and Carter" have shown that the presence of molybdenum greatly reduces the equilibrium extent of the change at a given temperature but does not appear to influence the rate of embrittlement. There appears to be very little information as to how molybdenum by itself affects the temper brittleness susceptibility of a plain carbon steel.

Jan 1, 1956

By C. W. Covington, H. C. Cook, J. F. Libsch

Sputtered aluminum thin films were prepared in each of two conventional bell-jar vacuum systems. One system utilized an inner "getter sputtering" enclosure; the second system was a standard diode sputterirlg arrangement. Consistent and repeatable film properties were obtained in both systems provided sufficient cleanup and presputter time was allowed. The various problems associated with aluminum sputtering are discussed, with pavticular attention to the vzinimization of film contamination by outgassing and oxidation. The growth and structure of the aluminum thin films were studied with the aid of electron wzicroscopy and related to deposition rate, substrate temperature, and film thickness. The resistivity of the films was correlated to film structure and surface roughness. Resistiuities as low as 3.5 microhm-cm (2.3 x bulk resistiuity) were measured for relatively thick films (20,000). THIS investigation was undertaken to explore the problems and film characteristics associated with the sputtering of aluminum. Earlier work reported on aluminum sputtering has stressed the contamination of both the cathode and film as well as abnormally low deposition rates.&apos; Data on sputtering yields,3 however, indicate that aluminum sputtering could be practical. Recently, it was shown by Theuerer and Hauser3 that aluminum sputtering was feasible in a conventional oil-diffusion pumped vacuum system provided an inner "getter sputtering" enclosure was employed to minimize gaseous contamination. This technique employs the getter action of aluminum to produce extremely low reactive gas partial pressures in the deposition zone. Aluminum films have already found use in solid-state electronic devices such as transistors and integrated microcircuits. To the present time, most aluminum films have been prepared by evaporation due to the ease with which this metal can be evaporated. Controlled sputtering of aluminum offers a number of advantages over evaporation, however, such as 1) manufacturing compatibility with other metals which must be sputtered, 2) better control of process variables resulting in more repeatable and uniform films, 3) generally better adhesion resulting from higher-energy metal atoms, 4) built-in material supply for continuous operation, and 5) the ability to deposit alloys. The data presented in this paper are the result of two separate studies. One study utilized a small "getter sputtering" enclosure (System A) and was concerned with the structure and properties of thin aluminum films up to about 1600A thick. In this thickness range, study of the film structure was possible with transmission electron microscopy. The second study was conducted with a conventional diode sputtering apparatus (System B) and covered $ much wider range of film thickness up to about 34,000A. Emphasis was placed on developing techniques which would extend aluminum sputtering to an existing in-line continuous deposition process.4 I) EQUIPMENT AND PROCEDURE System A. Fig. 1 shows a schematic of the "getter sputtering" inner chamber used and Fig. 2 is a photograph of this chamber mounted on an 18-in. access ring of a standard liquid-nitrogen trapped bell-jar vacuum system. This chamber was designed after a similar system used by Theuerer and auser.3 The configuration allowed the glow to emanate in all directions from the cathode. Argon (99.99&apos;) was allowed to enter only at the top of the chamber such that most of the reactive gases entering with the argon were reacted with the aluminum vapor and deposited on the chilled walls of the chamber before reaching the deposition zone. Provision was also made as shown, Fig. 1, for heating and cooling the substrate from about 20" to 400°C. Two substrate materials were used: Corning 7059 glass (12 by 12 by 0.048 in.) and carbon films about

Jan 1, 1967

By DeVerle P. Harris

Risk for most mineral investments is greater than that of average business ventures, because the physical and economic characteristics of the mineral deposit are never known with certainty. Inasmuch as the merits of a potential mineral investment cannot be fully appraised without consideration of the impact to the investor of the possible unfavorable events associated with the adoption of the project, methods of risk analysis are important in project evaluation and investment selection. The conceptual framework for risk analysis and the means by which some of the recommended practices might be implemented are examined. In addition to the normal business risk due to market forces, the physical and economic characteristics of the mineral deposit are never known with certainty, for only partial or indirect information is available, such as data from drill cores or surface and underground workings. Consequently, risk for most mineral investments is greater than that of average business ventures. Inasmuch as the merits of a potential mineral investment cannot be fully appraised without consideration of the impact to the investor of the possible unfavorable events associated with adoption of the project, methods of risk analysis are important in project evaluation and investment selection. This paper examines the conceptual framework for risk analysis and means by which might be implemented some of the recommended procedures. Utility Theory A discourse on risk and its impact upon investment selection quite often leads the reader into the concept of utility theory, for utility theory is a device constructed by economists to measure the satisfaction an individuai receives from a good; in the case of investment analysis, that good is the outcome of an investment. It briefly is reviewed here to describe the reaction of the individual to risk and as a stepping stone to other techniques more suited to risk analysis at the level of the firm. Utility theory proposes that an investor possess a utility map (curve), such as indicated in Fig. 1, which indicates the value in utiles of potential monetary rewards to an individual with some specific endowment of resources. Points on this map are obtained from the following relationship:

Jan 1, 1971

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th&apos;rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling&apos; in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By Anson Hayes, John Chipman

The quality of sheet and strip products made of rimming steel is closely related to the structure and chemistry of the ingots. The variation in composition throughout the ingot, as affected by segregation, is of great importance, as are also the form and distribution of the voids that result from the gases evolved. It is because of this importance that the considerable literature in this field has accumulated. No attempt is made in the present paper to compile a bibliography of the excellent work that has already been done, as this has been adequately covered in the many excellent reports on the heterogeneity of steel ingots prepared by a joint committee and published by the Iron and Steel Institute.&apos; From time to time, in any field of investigation new tools and new technique are developed, which make further progress possible. In the field with which this paper is concerned, this is true. The development of the vacuum-fusion method as a means of following oxygen segregation, and a technique for obtaining the volume and composition of the gases evolved during solidification, have opened the way to obtaining data by means of which some considerable progress has been realized in developing more of the detailed mechanisms of solidification and segregation in rimming-steel ingots. General Theory of Segregation The basic cause of segregation lies in the fact that the impurities are less soluble in solid than in liquid iron. The solid that forms from the impure liquid is more nearly pure than the liquid itself. If solidification proceeds slowly enough, or if the liquid and solid phases are maintained in contact with one another for a sufficient time, a condition of equilibrium is set up, which may be represented by a phase diagram. Portions of the

Jan 1, 1939

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein&apos;s study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,&apos; and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By W. A. Backofen, D. Lee

Titanium of commercial purity (RC-70) and two all-a (hcp) alloys (4Al-1/4O2 and 5Al-2.5Sn) were tested in sheet form under conditions of combined-stress loading. Plane-strain compression and plane -strain tension together with uniaxial compression and tension provided information for constructing the tension-tension and compression-compression quadvants of the plane-stress yield locus. Coordinate values were obtained from yield-strength measurements; the slope at each point was based on a plastic-strain ratio. The materials represented a wide range of plastic anisotropy, which was reflected in correspondingly varied departures of the yield locus from that for iso-tropy. The tension-tension and compression-compression quadrants were not identical. If the uniaxial yield strength is insensitive to direction and the sign of the applied stress, the Mises or perhaps the Tresca criterion is adequate for predicting the onset of yielding under combined-stress loading. The prediction is not so straightforward in plastically anisotropic material. Depending upon details of texture, combined-stress yielding resistance may be substantially different from that indicated by the usual criteria.&apos; However. a continuum theory of yielding under such conditions is available for reasonably direct application.2,3 Whether or not it can be used successfully must, of course, depend upon how closely the conditions of the theory are satisfied in the material in question. In its present form the theory contains no provision for Bauschinger-type effects, nor does it allow for the consequences that might grow out of deformation by more than one mechanism, e.g., by slip and twinning.4 With those limitations, more importance must be attached to experimental information about the yield surface for anisotropic materials. Studies of the yield surface have generally been confined to states of plane stress (tension-tension and tension-compression) established in thin-wall tubes by externally applied forces and internal pressure. That approach would be entirely suitable for anisotropic materials if they were available in tube form or in sufficient bulk to be machined into test specimens. 6-9 It would not serve for the textured and anisotropic sheets of much current engineering interest, unless sheet could be formed into high-pressure tubing without structural change. Since there would seem to be little chance of the latter, practical alternatives are needed. One such alternative is the subject of this paper. It involves the use of a few selected but relatively simple uniaxial loading tests on sheet specimens. The underlying idea is presented here with some details relating to application and a few results bearing on how well it has worked. THE BASIS OF TESTING Conventional Measurements. Yielding for a general case of anisotropy is described by the plane-stress locus in Fig. 1. Reference directions in the sheet specimen are related to the stress coordinates as shown with the insert: x is the rolling direction, y the transverse direction, and z the through-thickness direction. The four reference-direction yield strengths (t, tension; c, compression), Xt, Xc, Yt, and Yc, are all different. Nine paths that can be followed in uniaxial loading experiments are identified. Paths 1, 2, 3, and 4 represent conventional tension and compression testing to establish Xt, Yt,.Xc, and Yc. Useful information also comes from the ratio of the transverse plastic-strain components associated with yielding and flow in conventional tension or compression. A condition to be satisfied in locus construction is that the plastic-strain vector be everywhere normal to the locus.10 The projection of the vector which would

Jan 1, 1967