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By W. L. Zeigler

The mill is a departure from gravity concentration and has gained a reputation for the low initial cost of erection, extreme simplicity and the low cost of milling on the refractory character of the ore which is treated. The structure is of heavy timbers with board walls and corrugated roofing. The floors are concrete and the general layout is of the ground floor only. All the machines are driven by individual motors and the transmission usually found in such a plant is entirely absent. (Fig. 2.) ORE The ore from the Galena mine is sheared Wallace quartzite replaced with quartz, siderite, pyrite, sphalerite, gray copper (tetrahedrite) and very fine-grained argentiferous galena. Much of the silver is undoubtedly associated with the gray copper, the amount, however, apparently varies with different localities in the vein. An average assay of the ore is 6.0 per cent. lead, 1.3 per cent. zinc, 0.3 per cent. copper, 17.5 per cent. iron and 4.5 oz. silver. The concentrates produced are of an average 53 per cent. lead, 40 oz. silver, 8 per cent. zinc and 11 per cent. iron, while the tailings are 0.5 per cent. lead, 0.4 oz. silver. With the present market for zinc no attempt is made to produce a zinc concentrate.

Jan 1, 1927

By Eric Jette

The nickel-chromium alloys form the base f for many industrial heating alloys, so that this system is of considerable practical importance. The literature on these alloys, however, contains much conflicting evi-dence, not only regarding the solubility limits of the terminal solid solu-tions at different temperatures but even regarding, the number of phases existing in the system. Part of the difficulty undoubtedly arises from the fact that chromium of sufficiently high purity has been available only during the last few years. A second and possibly even more impor-tant difficulty arises from the ease with which chromium reacts with silicon and carbon compounds and the atmosphere to form silicides, carbides, nitrides and oxides. Pilling and kihlgren1 in 1929 reviewed the existing scanty information. They did not consider the diagram by which they summarized the various bits of information to be entirely satisfactory. Matsunaga2 investigated the system by thermal analysis, microscopic examination and other means. Electrolytic nickel of 99.9 per cent purity and thermit chromium containing 0.30 per cent al, 0.40 per cent fe, 0.25 per cent si and 0.04 per cent c were used. A tammann furnace with hydrogen flowing through it was used for melting. Sekito and matsunaga3 reported an x-ray, investigation presumably on these same

Jan 1, 1934

By Robert A. Rapp

The standard molar free energy of formation of MOO,was determined between 750o to 1050o C in galvanic cell measurements involving the solid electrolyte Zr0.85 Ca0.15 O1.85. Use of the reference electrodes Fe + FexO and Ni + NiO Provided two independent determinations of FoMoo2. The data may be represented by the equation FMoO2 = -137,500 +40.0T(°K) which is in good agreement with previous CO/CO, gas equilibrium measurements of Gleiser and Chipman. The standard molar free energy of formation of molybdenum dioxide has recently been reported over a large range of high temperatures from the calorimetric experiments of King, Weller, and christensen.' Gleiser and chipman2 have also recently determined ?FmoO2 from 926o to 1068oC in CO/CO2 gas equilibrium measurements. Earlier gas equilibrium studies have been made and reviewed by Gokcen.' Over the temperature range studied by Gleiser and Chipman their values for ?FoMoO2 differed from the calorimetric data by about 700 cal. This investigation was undertaken to resolve this difference and thereby establish the two phase mixture of Mo + MOO, as an electrode of well-known oxygen potential for galvanic cell applications at very high temperatures. The galvanic cell technique involving the Zr,.,, Ca,0.15 01.85 solid electrolyte was introduced for the

Jan 1, 1963

By H. A. Schwartz, A. F. Gorton, H. R. Payne

In a previous paper1 we published what we believed to be a correct stable equilibrium diagram for an iron-carbon alloy containing + 1.20 per cent. silicon. The purpose of the present paper is to record the results of studies concerning the effect of silicon on the location of the eutectoid points of both systems, including also certain incidental observations of general interest. We prepared white cast irons containing roughly 21/2 per cent. carbon, 0.05 per cent. manganese, and 0.03 per cent. each of phosphorus and sulfur, but of accurately known silicon contents which varied from 0.40 to 3.32 per cent. These were completely graphitized, and both A1 points determined, as in our previous work, the specimens being converted from the stable to the metastable condition and vice versa by appropriate heat treatments. Each stable alloy was heated to a few degrees above Arl for 3 to 7 hr., quenched and analyzed for total and graphitic carbon, the difference being the "combined" or, better, agraphitic2 carbon content of the saturated solid solution just above the eutectoid transformation. One specimen was lost through accident, and the 0.40-per cent. silicon material gave an anomalous result ascribed to difficulty in maintaining the stable system in the presence of but little silicon.

Jan 1, 1923

By H. R. Payne, A. F. Gorton, H. A. Schwartz

In a previous paper1 we published what we believed to be a correct stable equilibrium diagram for an iron-carbon alloy containing + 1.20 per cent. silicon. The purpose of the present paper is to record the results of studies concerning the effect of silicon on the location of the eutectoid points of both systems, including also certain incidental observations of general interest. We prepared white cast irons containing roughly 21/2 per cent. carbon, 0.05 per cent. manganese, and 0.03 per cent. each of phosphorus and sulfur, but of accurately known silicon contents which varied from 0.40 to 3.32 per cent. These were completely graphitized, and both A1 points determined, as in our previous work, the specimens being converted from the stable to the metastable condition and vice versa by appropriate heat treatments. Each stable alloy was heated to a few degrees above Arl for 3 to 7 hr., quenched and analyzed for total and graphitic carbon, the difference being the "combined" or, better, agraphitic2 carbon content of the saturated solid solution just above the eutectoid transformation. One specimen was lost through accident, and the 0.40-per cent. silicon material gave an anomalous result ascribed to difficulty in maintaining the stable system in the presence of but little silicon.

Jan 1, 1923

By Colin Rae

THE absence of paraffin and other oil hydrocarbons in the soil, although they are concentrated in extensive deposits in some localities, the common distribution of plant remains through many formations that .are not productive for oil, and many other factors, seem to indicate the existence of an intermediate organic compound between the complex plant compounds and the petroleum hydrocarbons; and much evidence points to the humus acids or associated organic compounds, which are probably collected by surface waters and concentrated in certain areas by means of precipitation by electrolytes, which would be contained in sea water or possibly in various inland seas or lakes. PRESENT-DAY EVIDENCE There are many present-day evidences of the association of petroleum with humus acids. Binney, in 1912, made observations without explanations on the peat mosses of Down Holland, England, where he found petroleum being formed by decomposition, in the presence of an infiltration of sea water. The analysis of a typical peat will show its relationship to the humus acids under consideration. SAMPLE 'No. 1, SAMPLE NO. 2, PER CENT. PER CENT. Water : 20.0 29.5 Ash 3.0 3.05 Fiber 47.0 54.95 Humus acids 30:0 12.50 J. D. Haseman and others have noted the association of asphalt and hydrocarbons with the swampy, boggy areas, particularly adjacent to the sea.

Jan 2, 1922

By James R. Cost

The increasing emphasis upon the use of refractory metals has resulted in a closer look at some of the properties of these materials. In the course of a study of the Nb-N system it became necessary to re-examine one such property, the spectral emissivity, e. Experiments were performed in order to determine e for solid niobium as a function of both temperature and nitrogen content. The results of these experiments, which indicate a small but significant correction to the spectral emissivity of pure niobium, are reported herein. In addition, data on the total emissivity, et, of niobium and the spectral emissivity of the nitride Nb2N are given. To this author's knowledge, neither of these emissivities are as yet reported in the literature. Previous studies of the spectral emissivity of niobium have been few. In 1915, Burgess and Waltenburgl obtained a value of 0.49. Whitney? in 1935, used a Mendenhall V to obtain the commonly accepted value of 0.374. A recent investigation of sintering of niobium graphically reported a value of about 0.36= using a solid block of the metal with a blackbody hole drilled into it. In the present experiment a method similar to that of Worthing4 was used. An 8-in. long and 3/16 in. diam hollow tube was formed from smooth surfaced 0.0013-

Jan 1, 1962

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

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

Jan 1, 1945

One of the best known of the early mining districts of Nevada was that at Eureka, where gold was first produced in 1864. While the most productive period for the district was during the early 1900s, production was maintained until World War II. During this time it is said that the Eureka district produced as much as $200 million from over 3,200 km (2,000 miles) of tunnels and workings. The Windfall Mine was discovered in 1902; and a 100 ton cyanide plant was operated there during the periods 1907 to 1912 and 1932 to 1940. Since 1974, however, Windfall Venture has been operating a unique heap leaching facility on the site of the old Windfall Mine. Gold at the Windfall occurs primarily in the Cambrian Hamburg dolomite which has been "sanded" and in which the original cementing material has been destroyed. The gold is micron sized and is accompanied by anomalous amounts of arsenic and mercury; however, the ore is low in base metals which distinguishes it from the typical Eureka district ores. Mining the ore causes it to break down into very fine sizes, approximately 50% minus 150 microns (100 mesh). Conventional heap leaching by spraying proved to be impossible; and extensive test work on alternate methods, aided by the United States Bureau of Mines, was conducted using 9 m (30 ft) high columns and then large tonnage heaps. The leaching procedure adopted was to build 10.6 m (35 ft) high heaps on a 50 mm (2 in.) asphalt pad covered with a layer of gravel for drainage assisted by perforated pipe drains and gravel-packed sumps. A berm is constructed around the top of each pad and cyanide solution is allowed to “pond” on top of the heap. The resulting percolation is at the rate of 24 liters per sq m per hr (0.6 gal per sq ft per hr), a figure about 2.4 times the average used in other heap leaching operations. The dolomite furnishes its own protective alkalinity and no lime or caustic is used in the solution which contains 0.4 kg per mt (0.8 lb per st) of NaCN. Pregnant solution from the heaps averages about 0.7 g Au per mt (0.02 oz per st) with a cyanide content of about 0. 2 kg per mt (0.4 lb per st) and a pH of plus 9. Addition of NaCN brings the pH of the leach solution up to 11 to 12. Carbon adsorption of the gold was originally done in six enclosed columns mounted in a trailer but five conventional columns have been substituted as the size of the operations has increased. Carbon stripping is with hot caustic, cyanide and 10% ethanol solution. The

Jan 1, 1981

By P. S. Kotval

THE nominal composition of "hconel" alloy 718 is 53 pct Ni-19 pct Cr-19 pct Fe-3 pct Mo-5 pct Cb-0.8 pct Ti-0.6 pct A1-0.05 pct C. The nature of the fine strengthening phase in this alloy has been open to debate. iseelstein' has identified the strengthening phase in the matrix of "Inconel" alloy 718 as a colum-bium-rich fcc y' precipitate. Wagner and Hall2 have noted that the metastable y' precipitate overages to an orthorhombic Ni3Cb precipitate which manifests itself as an acicular phase. These authors thus clarify Kaufman and Palty's earlier suggestion3 that the strengthening phase is orthorhombic NisCb. Wagner and Hall's review also reports work by cometto4 which suggests that the fine strengthening phase is not fcc / but bct with a Ni3V type structure and based on the Ni3Cb composition. Kir man and warringtons have shown by analysis of electron diffraction patterns that the metastable strengthening phase in a 55 pct Ni-15 pct 0-25 pct Fe-5 pct Cb alloy is bct and based on the Ni3Cb composition. Raymond~ has provided electron diffraction evidence which indicates that "y'" in "Inconel" alloy 718 is bct in structure. This note presents unambiguous data on the structure of the strengthening phase in "Inconel" alloy 718* ihe samples of this alloy were provided by courtesy of the ASTM task group on phase identification in 'superalloys. after prolonged aging. The electron diffraction patterns presented show that strengthening phase is not y' but bct as was proposed by cometto,' supported by Raymond,~ and identified by Kirman and warringtons in a similar system. Fig. 1 shows a selected-area diffraction pattern taken from a thin foil of "Inconel" alloy 718. The sample had received a final aging treatment of 1118 hr at 1200°F to precipitate the strengthening phase in the matrix. Fig. 2 is a schematic representation of the features in the diffraction pattern. The matrix orientation is (0i2)~,, as is shown by the indexed zone in Fig. 3. Figs. 4, 5, and 6 illustrate that the pattern, Fig. 1, is composed of three bct zones, viz., (0i4), (2i0), and (i01), respectively. These three zones correspond, respectively, to the alignment of the c axis of the bct unit cell with the [001], [loo], and [OlO] directions of the fcc matrix and serve to illustrate the fully coherent relationship of the precipitate structure with the matrix. The streaking of certain reflections is also consistent with the above orientation relationship. The interpretation of the diffraction effects presented here shows the metastable strengthening precipitate in "Inconel" 718 alloy to be bct in structure and demonstrates that it is not an ordered fcc y' phase.

Jan 1, 1969

By Yoichi Ishida, Ching-Yao Cheng, John E. Dorn

Tile creep behavior of a iron was investigated over the range of temperatures from 375° to 1150°K. Apparent activation energies for creep, obtained by the effect of sudden changes in temperature on the creep rate, revealed the presence of- four distinguishable regions. The creep behavior of a iron in Regions II (480° to 774°K) and 111 (775° to 1045°K) was found to correlate well with a model where the creep rate is controlled by the nonconsevualive motion. of jogged screw dislocations. An anomalous increase in the apparent activation energy fur creep in Region III was found to be in harmony with the known decrease in the free activation energy for self-diffusion over the Curie transformation range. Furthermore, the creep rates in Regions II and III were found to increase with stress due not only to the effect of stress on the activation energy but also to an increase in density of mobile dislocations. The evidence suggests that pipe diffusion along moving dislocations could be a significant factor over the lower temperatures of Region II. ALTHOUGH the creep properties of iron and steel have been of interest to metallurgists for some time and an extensive literature is now available, most of the published information has not produced much toward understanding the fundamental dislocation processes controlling the creep behavior of these materials. Whereas the activation energy for high-temperature creep of metals usually agrees well with that for self-diffusion, Sherby, Orr, and Dorn1 deduced from the data of Tapsell -and c1enshaw2 that the activation energy for creep of Armco iron is about 78,000 cal per mole and more recently Lytton and sherby3 reviewed the data of Jenkins and Mellor4 and found an activation energy for creep of a iron of 80,000 cal per mole. Both values are substantially greater than the activation energy for self-diffusion in a iron. Because of the limited data suitable for purposes of identifying the controlling dislocation mechanisms of creep and the unusually high activation energies for creep quoted above, it was considered desirable to reinvestigate in detail the creep of a iron by more reliable techniques which would provide sufficient data for determination of the creep mechanisms. EXPERIMENTAL TECHNIQUE Creep specimens were prepared from 3/8 by 4 in. iron bar stock of the following composition by weight percent: 0.001 C, 0.0120 0, 0.001 N, 0.004 S, and 0.003 P. The as-received bars were cold-rolled to a thickness of 0.100 in., annealed under argon for 30 min at 1113°K, cold-rolled to a final thickness of 0.063 in., and machined into tensile specimens having gage section 0.250 in. wide and 1.70 in. long. Finally they were recrystallized under argon at 1113°K. Specimens to be crept above 1060°K were recrystallized at 1173°K. Both recrystallization treatments gave the same reproducible equiaxed ASTM No. 4 grain size. Creep testing was conducted in machines fitted with Andrade-Chalmers arms that maintained a constant stress to within ±0.2 pct of the reported values. Deformation over the specimen gage section was sensed with a linear differential transformer and recorded auto-graphically as a function of time. The strains deduced from these measurements were sensitive to ±5 x 10-5. During creep the specimens were contained in an argon-filled chamber which was immersed in a temperature-controlled molten tin bath. Creep temperatures, as measured by thermocouples attached to the specimen, were maintained to within ±10.25°K of the reported values. For activation-energy determinations rapid changes in temperature of about 12°K were obtained within 30 sec by direct resistance heating of the creep specimen, and maintained to ±1°K of the reported values. Observations of structural details of specimens before and after creep tests were made by electrolytic polishing and etching in acqueous ammonium persulfate. EXPERIMENTAL RESULTS A typical example of the determination of apparent activation energies, Q, by the effect of small changes in temperature is illustrated in Fig. 1. Q is defined by

Jan 1, 1967

By Paul A. Farrar, Sanford Adler

The Tz-Zr system was reinvestigated using both metallographic and X-ray diffraction techniques. It mas found that titanium and zirconium are soluble in all proportions in both the a and 0 phases. The minimum in the transformation was found at 50 at. pct and 535°C. THE Ti-Zr system has previously been the subject of several investigations.1-6 A study by Hayes et al.5 using magnesium-reduced titanium and zirconium melted in graphite crucibles indicated that the system was a continuous series of solid solutions in both a and 0 phases with a minimum at approximately 545°C and 65 pct* Zr. These conclusions were substantiated by the work of Duwez4 as well as by the limited data of Craighead et al.,3 Fast,2 and deBoer.1 However, a more recent investigation of the titanium-rich region by Ence and Margolin6 indicated that the solubility of zirconium in a, titanium at 500°C is approximately 22 pct with the a + 0 field extending to approximately 47 pct Zr. Therefore in order to resolve this discrepancy the following investigation was initiated. EXPERIMENTAL PROCEDURES The alloys used in this investigation were prepared as 20- to 30-g buttons by nonconsumable electrode melting in a helium atmosphere. The starting materials were Bureau of Mines titanium BHN 71 and Foot Mineral iodide crystal bar zirconium. The titanium was premelted before the alloys were prepared to avoid excessive weight losses in the final melting. The compositions of the alloys prepared were as follows: Ti-12.0, 22.2, 29.0, 39.6, 50.0, 58.0, 72.4, 83.5. and 90.8 pct Zr. Prior to heat treatment the alloys were cold-worked 10 to 20 pct, stopping at the first signs of cracking. Specimens for heat treatment were wrapped in molybdenum sheet and annealed in argon-filled quartz capsules for the following times and temperatures: 750°C-40 days, 675°C-61 days, 600°C—109 days, 575°C-112 days, 550°C-112 days, 525°C—127 days, and 450°C —153 days. Quenching was accomplished by breaking the capsules in an iced-brine solution. The standard techniques used for polishing the specimens involved belt grinding, grinding on emery paper, polishing electrolytically, and etching with Remington "A" etch7 or "R" etch 8 Debye-Scherrer X-ray powder photograms were obtained for a number of samples using a 114.6-mm camera and CuK, radiation. Exposure times were from 19 to 23 hr. The powder samples were obtained by filing to 270 mesh size. After filing the samples were wrapped in molybdenum foil capsuled in quartz and reannealed at the temperature of original heat treatments; following the heat treatment the samples were quenched into iced brine without breaking the capsules. RESULTS AND CONCLUSIONS On the basis of the microstructural examinations of the heat-treated samples and of the X-ray diffraction data, the Ti-Zr system shown in Fig. 1 was constructed. The data indicate that a, and 0 titanium form a complete series of solid solutions with a, and ß zirconium. The minimum was found to occur at 65 pct (50 at. pct) Zr and 535°C, in excellent agreement with the earlier investigations,1-5 see Fig. 2. Typical microstructures are shown in Figs. 3 to 7. Figs. 3, 4, and 5 show the 22.2, 39.6, and 50.0 pct Zr alloys after heat treatment at 675°C for 61 days with the 22.2 pct Zr showing equiaxed a, and the 39.6 pct Zr alloy a + transformed ß, while the 50 pct Zr alloy shows only transformed B. Figs. 6 and 7 show the 29.0 and 39.6 pct Zr alloys after heat treatment for 109 days at 600°C. The 29 pct Zr alloy has an equiaxed a structure while the 39.6 pct alloy has a partially recrystallized a+ß structure. X-ray diffraction data obtained from the 50 pct Zr alloys after heat treatment at 525° and 450°C as well as from the as-cold-rolled material showed only those lineos which couid be indexed a: a titanium, good agreement with the previously published values. 2,4,5,9 Chemical analysis* of the 50 pct Zr alloy

Jan 1, 1967

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By H. L. Marcus, C. D. Turk

Titanium was physically vapor-deposited by electron beam high rate evaporation. Rates of 50,000 and 85,000Å per min at deposition temperatures of 480°, 535°, and 595°C were used. Deposited thickness ranged front 0.004 to 0.010 in. The evaporated titanium had a high degree of basal Plane texture. The specimens were tested in tension at temperatures ranging from 78° to 520°K. From the data, the yield stress, thermal component of the yield stress, and work hardening characteristics were found as a function of temperature, deposition rate, and deposition temperature. It was found that Taylor's equation, best fit the work hardening data with m = 1/2. MANY investigations have been made on the tensile deformation characteristics of commercial- and high-purity titanium.1"7 The data obtained from these experiments emphasize the fact that the mechanical properties are generally related to the method of production. The correlation of mechanical properties to production history arises from the dependence of impurity concentration on the extraction and melting technique used. Additional effects are derived from crystallographic texturing which can result from fabrication history. Lee and Backofen8 and other investigators9 have shown that crystallographic texturing in titanium sheet has a significant effect on the deformation characteristics. Bunshah and Juntz10 prepared high-purity titanium by high rate physical evaporation techniques. These authors found the deposited material to have a columnar structure with grain sizes ranging from 12 to 104 µ, depending upon the substrate temperature. The room-temperature strengths of the coarse-grained distillate were similar to arc-melted, rolled. and annealed crystal bar titanium. Commercial-purity titanium was also produced experimentally in our laboratory using high rate physical vapor deposition techniques. The commercially pure material has a finer structure than the high-purity distillate,10 and is highly textured. Since the method of preparation and degree of texturing affect the mechanical properties, a research program was initiated to determine the temperature dependence of the yield stress and work hardening characteristics as a function of high rate deposition parameters. This paper relates the results of the investigation. EXPERIMENTAL A) Material Preparation. The titanium was received in the form of commercial-grade 0.096-in.-diam wire which has a composition of 0.016 pct C, 0.0037 pct N, 0.110 pct 0, 0.011 pct H, 0.05 pct Mn, 0.051 pct Fe. balance Ti. The wire was continuously fed into a vacuum evaporation unit as shown schematically in Fig. 1. The deposition chamber was evacuated, purged with argon, and reevacuated to a pressure of 10-5 Torr which was maintained during deposition. A focused electron beam was used to evaporate the titanium from a water-cooled copper crucible. The titanium vapor was condensed onto a preheated titanium substrate. The temperature of the substrate was controlled within ±5°C for the deposition temperatures of 480°, 535°, and 595°C. Control of the input power enabled the use of two deposition rates. 50,000 and 85,000Å per min. The evaporated titanium had a final analysis similar to that of the input titanium, within experimental limits. B) Testing. The evaporated titanium was physically stripped from the titanium substrate and machined into tensile specimens with 1-in. gage lengths. In addition, tensile specimens of as received annealed 35-A titanium sheet with a 20 µ grain size and 45 pct cold-rolled 35-A were also prepared. All specimens were tested in tension in an Instron at a strain rate of 3.3 x 10"4 in. per in. per sec. Proportional limit has been used as a measure of yield strength. Tests were conducted at 78°, 220°, 300°, and 520°K. Metallography, X-ray diffraction, and electron microscopy were used to correlate structure with the deposition parameters and mechanical properties. Room-temperature X-ray measurements were made to determine the phases present. Pole figures and a scans were made to determine deposition texture. Because the vapor deposition was symmetrical about the normal to the substrate, there was no preferred di-

Jan 1, 1969

By R. W. Freeman, L. L. Tavlarides

The experimental methods used in obtaining kinetic data for solvent extraction systems can affect the validity of the results The method of contacting the two liquids should allow for accurate determination of the surface area, hydrodynamics, and diffusional processes The appropriateness of the Liquid Jet Recycle Reactor is discussed and the modelling of the mass transfer and chelation reaction is presented The LJRR is used to investigate the chelation of copper by LIX65N in toluene from aqueous copper sulfate sulfuric acid solutions The ranges of experimental variables are Copper, 1 8-13.8 g-dm-3, sulfuric acid 0-1.6 g-dm-3, LIX65N, 0 1-1.0 mol-dm-3 Data on the initial rate of copper chelation at the interface is generated Nonlinear regression analysis shows that the following expression adequately describes the data within experimental error.

Jan 1, 1981

By J. L. Wyatt

THE strain sensitivity, K, a property of metals defined as the unit change in electrical resistance per unit strain, was measured for commercial purity titanium wire to determine its usefulness as a strain gage material. A Kelvin double bridge, accurate to 0.000001 ohm, was used to make measurements from 0 to 1 pct total strain. A positive value of 0.17 for K was found. This compares with 2.15 for constantan and 3.5 for cold-worked invar, two of the more common strain gage materials. The effect of temperature also was determined. It was found that a change in temperature of 30°F caused the same resistance change as 1 pct strain. It is therefore concluded that titanium would have utility as a strain gage only if the thermal fluctuations in the specimen could be controlled to a high degree and in applications of very large total strain.

Jan 1, 1953

By A. R. Marder

Fe-C alloys have been investigated at temperatures below the eutectoid transformation to determine whether the superplasticity phenomenon exists for these materials. As a result of void formation at the carbide-ferrite interfaces that led to void coalescence and premature failure, the large elongations characteristic of superplustic matem'als did not develop. It had generally been assumed that the conditions for obtaining superplasticity include: a) T/Tm =0.5, b) a strain rate sensitivity of the flow stress that results in m s 0.3, and c) fine-grain structure. Although superphsticity was not observed in the alloys studied, stress-strain rate measurements indicated that an additional condition for the existence of superplasticitv in Fe-C allovs is that the fine-wain structure be equiaxed in agveement with previous results on Zn-Al al1oys. MANY investigations have been made on the hot deformation of iron-base alloys in order to obtain an understanding of the variables that may affect high-temperature strength and ductility.'-6 However, only a few papers have studied the effect of carbon content on the high-temperature properties of iron-base alloys. Peretayat'ko and Zaikov and Wallquist and carlen4 studied the effect of carbon on strength in the y temperature range, and recently Robbins, Shepard, and sherby6 studied the influence of carbon on the torsional behavior of iron in the a and cu-plus-cemen-tite temperature ranges. In addition to studying hot deformation behavior, current investigations have also been concerned with the phenomenon of superplasticity in nonferrous materials, and, in particular, ferrous alloys. Superplasticity is identified by the increased resistance to necking that results from a high strain rate sensitivity of the flow tress. ackofenr proposed the strain rate hardening coefficient m = d log a/d log e as a measure of strain rate sensitivity and showed that m must be "-0.3 for superplasticity to exist. In addition, a fine-grained microstrcture,- a eutectic or eutectoid ornosition,- and a test temperature in the creep range (TITm > 0.5)" have also been advanced as necessary conditions for superplasticity. Although many workers""23 investigated superplasticity associated with the allotropic transformation in iron and the eutectoid transformation in steel, and recently chadler " and orrison have studied superplasticity in the a - y phase region, no one has measured the superplastic effect in the a + cementite temperature region. Therefore, the purpose of this investiga- tion was to determine the effect of carbon content, microstructure, and test temperature on the strain rate sensitivity of Fe-C alloys at temperatures below the eulectoid transformation. EXPERIMENTAL PROCEDURE Fe-C alloys with carbon contents of 0.2, 0.4, 0.6, 0.8, and 1.0 wt pct were prepared as 100 lb 54 in. ingots by vacuum-induction melting. The compositions are listed in Table I. All the ingots were soaked at 2100°F for 2 hr prior to rolling to 4 in. plate. The minimum finishing temperature for rolling was 1800°F. The plate was sheared in 10-in. lengths and tensile bars were rough-machined prior to heat treatment. The samples were heat-treated according to the schedule in Table I1 in order to obtain a fine-grained microstructure consisting of finely dispersed carbides in a matrix of small ferrite grains. All the tensile specimens were heat-treated prior to finish machining, and tensile testing was accomplished on an Instron machine in conjunction with a clamshell furnace. The buttonhead specimen configuration is shown in Fig. 1. An inert atmosphere, helium, was maintained during testing with a steel tube shroud in a bell jar arrangement. Predried helium was continually purged over the buttonhead specimens and exhausted through ceramic fiber at the bottom of the tube to keep oxidation at a minimum and to prevent

Jan 1, 1970

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

By J. E. Miller, W. E. DeVaney, L. Stroud

During a recent phase study of a natural gas, two stable equilibrium liquid phases were observed at temperatures below —200°F and pressures above 200 psi. This paper reviews the published literature on the occurrence of multiple equilibrium liquid phases and presents analytical data for the vapor and two equilibrium liquid phases of the liquefied natural gas at five experimental conditions. In addition, data for 30 conditions of two-phase equilibria are included. INTRODUCTION The low-temperature phase behavior of gases, most of which contained helium, has been investigated in the laboratories of the Helium Activity for many years. Since 1952, experimental studies of these systems have been continuous as part of the research program at Amarillo, Tex. Because of their value to private industries interested in participating in the Helium Conservation Program, several "Open File" reports containing phase equilibria data for heliurn-bearing natural gases have already been released by the Helium Activity. A paper containing information on the general phase behavior, operating criteria and extensive vapor-liquid data for two helium-containing systems was recently published.2 Additional publications presenting experimental data on the phase relationships of various gas systems are now in process and will be available in the near future. PREVIOUS EXPERIMENTAL WORK Although the formation of multiple liquids has been reported for various systems, to our knowledge this paper is the only substantiated evidence of a vapor-liquid-liquid equilibria in a naturally occurring gas. In 1940, Vink, Ames, and others13 reported the presence of two liquid phases in a hydrocarbon system consisting of mixtures of crude oils, solvents and natural gas. Eilerts and co-workers; published data on the recombined fluids from a gas-condensate well. This condensed gas, containing approximately 76 per cent methane and 24 per cent ethane-plus, exhibited two distinct liquid phases. Weinaug and Bradley 14 observed "unusual" phase behavior in a reservoir mixture. These workers postulated that the anomalous phase behavior was due to the "imminent formation of a second liquid phase". Botkin, Reamer, Sage and Lacey 1 studied two California crude oils that exhibited multiple phases. Kohn and Kuratal0 recently reported two equilibrium liquid phases in the methane-hydrogen sulfide system. Roof and Crawfordl1 and Eakin, et a16 also have reported experiments with binary systems that formed two stable equilibrium liquid phases. APPARATUS AND PROCEDURE A U. S. Bureau of Mines Phase Equilibrium Apparatus was used in conducting this study. The apparatus and procedures employed in its operation have been previously described3 and will not be repeated in detail ill this report. Briefly, the apparatus consists of a windowed cell which can be maintained within ±0.5°F for temperatures between room temperature arid -320°F. Pressure within the cell can be maintained within 0.1 per cent of gauge reading up to 800 psig. Equilibrium vapor and liquid samples are obtained in special containers4 for analysis by a mass spectrometer. Although the accuracy of the analyzer is about ±0.1 mol per cent, the reproducibility of the phase-equilibrium apparatus is considered relatively poor. Values reported from methane and nitrogen are considered accurate to ±l.0 and ±0.6 mol per cent. Data for ethane-plus in the vapor are accurate within 0.2 mol per cent; liquid-phase data for this aggregate compolnent are accurate within 1.5 mol per cent. For helium in the vapor phase, the analytical data are accurate within 0.2 mol per cent; liquid-phase analyses for this component were obtained by the charcoal adsorption method described by Frost8 and are accurate within 0.006 mol per cent. All of these references to the accuracy of reported values are conservative estimates based upon a statistical treatment of reproducibility data obtained with the apparatus.

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953