Search Documents

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

It is known that stoichiometric NiTi transforms to a structure of lower symmetry near room temperature. The present investigation deals primarily with the changes in the electrical and magnetic properties which occur at the transformation. The effects of composition and various heat treatments on electrical properties are also discussed. In recent investigations by Purdy and Parr,' Wang et a1.,2 Dautovich and Purdy,~ Dautovich et a1.,4 and the authors, ~,' NiTi has been observed to undergo a martensitic phase transformation from the ordered CsCl (B2) structure to one of lower symmetry. The crystal structure of the low-temperature modification is still not completely worked out. This transformation occurs near room temperature for the stoichiometric composition. The thermodynamic, elastic, crystallographic, and microstructural characteristics of this transformation for some compositions have been previously reported.'-= In the present investigation, the changes in the electrical transport properties and magnetic susceptibility of NiTi when it undergoes the martensitic phase transformation have been measured. The approximate composition range covered is 48 to 52 pct Ti.* *All compositions are given in atomic percent._____________________ EXPERIMENTAL PROCEDURES AND RESULTS 1) Sample Preparation. The NiTi alloys were prepared from iodide titanium (>99.92 pct Ti) and vacuum-premelted carbonyl nickel (>99.95 pct Ni) by repeated arc melting under gettered argon and casting in a water-cooled copper mold. After the cast buttons were hot-forged at 800" to 950°C, the oxidized surface was removed by grinding and etching. Samples were cut from the worked polycrystalline buttons. After fabrication, the samples were annealed 1 hr at 900°C and water-quenched. The composition of the alloys was assumed to be the same as in the initial feed. This assumption was supported by material balance checks on 100-g arc-melted buttons which demonstrated quantitative recovery to within k0.02 pct. The oxygen content of the alloys was '150 ppma (weight) and the carbon content was 30 to 50 ppm. 2) Electrical Resistivity and Hall Effect. The electrical resistivity was measured over the composition range 48 to 52 pct Ti for temperatures varying from 4.2"K to 900°C. The high-temperature and many of the low-temperature experiments were carried out using conventional 4-probe dc techniques.7 The Hall coefficient and ac resistivity were measured at 20 cps using the apparatus shown schematically in Fig. 1. The equipment is basically an ac potentiometer: The resistive or Hall voltage of the sample is balanced by a comparison voltage provided by a dividing network across a standard series resistance. The off-balance signal is amplified by a Tektronix 122 amplifier and detected by a Princeton Applied Research (PAR) phase-sensitive detector. The precision of the resistivity and Hall coefficient measurements is i0.1 and i3 pct, respectively. The uncertainty in the data is increased by i2 pct from the precision limits because of uncertainty in dimensions and possible end effects. The temperature dependence of the electrical resistivity and Hall effect for a stoichiometric (50.0 pct Ti) NiTi sample are illustrated in Fig. 2. Above 75"C, this sample has essentially the B2 structure, while below about 0°C it is completely in the low-tempera-

Jan 1, 1968

By M. C. Smith, W. V. Green, D. M. Olsen

The creep-rupture behavior of commercial powder-metallurgy molybdenum rod is reported in the temperature range 1600" to 250O°C, at stresses up to 9000 psi and times up to 1 month. The effects of temperature, stress, and grain growth are discussed. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher-stress results reported by pugh.1 BECAUSE of its high melting point, molybdenum should retain useful strength to relatively high temperatures. Combined with its ready availability in the United States, this makes it attractive for many applications in missiles, rockets, and so forth—wherever its susceptibility to oxidation can be tolerated or overcome. The mechanical properties of molybdenum rod in the temperature range —200" to 1540°C have been reported by pugh,' Bechtold,' Parke,3 and Carriker and Guard.4 Madden and chen5 have measured the tensile properties of molybdenum single crystals in vacuum up to about 2500°C. As one further step in evaluating its mechanical usefulness, the constant-load creep-rupture properties of commercial powder-metallurgy molybdenum rod have been investigated in the range 1600" to 2500°C. MATERIAL TESTED Creep specimens were machined from 1/2-in. round commercial molybdenum rod, manufactured from powder by pressing, sintering, and swaging. Spectrochemical analysis of the rod showed "traces" (less than 0.01 pct) of silicon, aluminum, chromium, iron, and zirconium, and "faint traces" (less than 0.001 pct) of manganese, magnesium, cobalt, and nickel. Carbon content was 130 to 200 ppm, nitrogen was 110 to 180 ppm, and oxygen 30 to 35 ppm. A typical microstructure of the as-received rod is shown in Fig. 1. Room temperature tensile properties for five specimens strained at about 0.015 in. per in. per min are shown in Table I. CREEP SPECIMENS USED The specimens used for creep-rupture testing are illustrated in Fig. 2. The 1/4-in.-diam gage section was 3/4 in. long, and terminated at shoulders 5 mils high. These shoulders served as fiducial marks for optical strain measurements. Surface finish on the gage section was 16pin. r.m.s. One specimen, for a "long-time" test described below, was modified by dividing the 3/4-in. gage length into three 1/4-in. long sections with individual diameters of 0.250, 0.230, and 0.210 in., each terminating in a pair of fiducial shoulders. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.6 In it the specimen is held vertically on the axis of a cylindrical tantalum or tungsten heater tube by threaded molybdenum or tungsten grips. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. The bottom specimen grip is held at its lower end by a clevis pin. The testing load is applied to the specimen through the upper grip by means of hanging weights, a constant force-multiplication lever system, and a pull rod sealed to the chamber lid by a bellows. The incandescent specimen is viewed by an external optical system through slots in the heater-tube and radiation shielding, and an enlarged image of it is projected on a ground-glass screen. Gage-length measurements are made on this image with a pair of cathetometers. Thorium oxide coatings were applied to the threaded ends of most specimens, to prevent diffusion-welding of specimens to grips during testing. Without such a coating welding usually occurred, and grips were often broken by subsequent efforts to remove the tested specimens.

Jan 1, 1960

By M. Yokoi, K. Yoshida, T. Ishihara

The solubility of aluminum in cryolite melts has been determined by measuring the weight loss of aluminum submerged in melts contained in closed silicon nitride crucibles. The solubility in pure cryolite has also been checked with radioactive isotopes. The solubility decreases with increasing A1203 concentration, decreasing temperature, and decreasing cryolite ratio. The change of aluminum solubility in pure cryolite with the activity controlled by using Al-Ag and A2-Cu alloys supported the assumption that aluminum would dissolve in the form of monovalent ions according to the reaction 2AI + A1' —3 A1'. DURING the electrolytic production of aluminum, the electrodeposited metal redissolves in the bath in some form and is subsequently oxidized back to the former ionic state. This dissolution is believed to cause a decrease in current efficiency. Reported data on the solubility of aluminum in cryolite melts are scattered. The mechanism of the dissolution has not yet been determined, although certain tentative interpretations have been proposed. Many previous studies were performed under different test conditions. Studies were performed in open Systems and closed systems,'o and some were apparently not given sufficient time to Saturate." The solubility can be determined either analytically or gravimetrically. The analytical determination involves measurement of hydrogen gas evolved when frozen cryolite bath saturated with aluminum is treated with sodium hydroxide or hydrochloric acid. The gravimetric determination, adopted by many investigators,'-37'3>14 involves measurement of weight loss of the metal after equilibration with a known amount of salt. It appears that the former technique yields much smaller values of solubility than the latter technique. This large difference in results strongly suggests that the dissolved metal in the cryolite melt is no longer in the metallic state. In the present study, the solubility was determined by the gravimetric technique at various activities of aluminum using A1-Ag and Al-Cu alloys. An attempt was also made to determine the ionic (or atomic) state of the dissolved metal from the solubility data. 1) EXPERIMENTAL Apparatus. Preliminary tests demonstrated that silicon nitride was suitable as a container material since it is compatible to both the fluoride melts and molten aluminum. Crucibles were made from silicon powder nitrided with Nz gas at 1600°C. The good compatibility between crucible and melts is due to the near perfect nitrogenation of silicon. Only small amounts of silicon were found in the aluminum metal after the experiments. The crucible dimensions were 90 mm inside height, 38 mm ID, 105 mm outside height, and 50 mm OD. Close-fitting lids made of silicon nitride were also prepared. The crucible was placed in a close-fitting graphite crucible heated by a vertical Kanthal furnace, Fig. l. The lid and crucible are fastened tightly together by the condensation of vaporized bath in the narrow gap between them. The temperature was measured in the wall of the graphite crucible and controlled within * 5°C. The temperature difference between the measuring point and the interior of the melts was initially determined. Materials. The materials used were: Greenland cryolite (impurities CaF,, 0.5 pct; AlzO3, 0.2 pct; high-purity aluminum metal (purity 99.99 pct); A1203 and AlF, (provided by Nippon Light Metal Co., Ltd); reagent-grade NaF and CaF2; and 99.9+ pct Ag and Cu. Powdered reagents were carefully dried before use. A1-Ag and A1-Cu alloys were prepared before the experiments; their composition was checked by analysis

Jan 1, 1969

By S. Shapiro, G. Krauss

RECENT investigations1 3 of the products of marten-sitic transformation in Fe-Ni and Fe-Ni-C alloys have made use of light microscopy to describe mar-tensitic fine structure. The application of conventional metallographic techniques to this problem was possible because of the similarity of distributions of parallel striations developed by etching polished surfaces to distributions of transformation twins which are positively identified in thin films by transmission electron microscopy. The surface striations frequently are not well-defined, and could also be due to, for example, rows of etch pits which are not resolved by the light microscope. This note describes the etching effects revealed by examination of surface replicas of mar-tensite in the electron microscope. The application of a replica technique both extends the observations of fine structure made with the light microscope and allows the results of conventional metallography to be used with more confidence. Samples of an Fe-33 wt pct Ni alloy were used for this study because of the detailed knowledge of the fine structure of martensite which has been developed'-4 for alloys of about this composition. Samples transformed to martensite at -120°C, and transformed samples heated to 340°C to effect a small amount of reversal of martensite to austenite, were examined. Surfaces were first prepared for replication by elec-tropolishing in a chromium oxide-acetic acid electrolyte at a current density of 0.1 amp per sq cm and a temperature of 15°C or a perchloric acid-acetic acid electrolyte at a current density of approximately 2 amps per sq cm and a temperature of 15°C. The polished surfaces were then etched for 4 to 7 sec by immersion in a solution of equal parts HC1, HNO,, and H20. Application of the etchant for this period of time produced discrete attack of certain features without loss of resolution due to overlapping of areas most susceptible to etching. The etched surfaces were replicated by 1) preshadowing with Pt-Pd alloy at an angle of 20 to 30 deg, 2) depositing a thin carbon film, and 3) stripping the film and shadowing material by immersion in a 5 pct nital solution. Two types of etching effects were observed by examination of the surface replicas in the electron microscope: l) continuous striations centered at the bottom of long grooves or the tops of pyramidal elevations on the sample surface, and 2) high densities of fine etch pits. Examples of both types of features are shown in Figs. 1 to 4. The striations are in each case continuous and have the same characteristic configurations as do transformation twins in martensite. Fig. 1 shows that the density of grooves decreases toward the edge of a martensite plate and Fig. 2 shows a region where the striations are of varying length. Similar examples of transformation twin arrangements determined by transmission electron microscopy of thinned foils of martensite have been shown in the literature,'~ and, based on these similarities, the striations and their associated grooves or mounds are considered to be evidence for the presence of transformation twins. The transf~rmation twins in martensite are on the order of l00 A thick, much too fine for resolution by the light microscope. It appears that orientation-dependent etching of the matrix martensite about the twins results in grooves or surface elevations which

Jan 1, 1967

By E. O. Wagner, V. F. Parry, J. B. Goodman

The low-rank coals containing 10 to 50 pct natural bed moisture represent over half of the tonnage reserve of the available solid fuels of the United States, but only about 2 pct of United States coal production is derived from these fuels. Increased utilization of these large reserves will result if the bed moisture can be removed at the mine in high-speed low-cost processes. This paper presents a theoretical and experimental study of the factors affecting high-speed drying of coal dusts. The time required to heat particles of coal is proportional to the square of their diameter, and it is calculated that the probable time in minutes is equal to 6D2. In other words, a 1/16 in. coal particle should be heated to drying temperature in 1.5 to 2.0 sec. Likewise, 1/8 in. particles should be heated in about 6 sec. The net heat required to dry subbituminous coal and lignite varies from 240 to 375 Btu per pound, depending upon the moisture removed, and this heat can be obtained from 42 to 61 cu ft of hot gases at 600°F. The necessary heat also can be obtained from 7.5 to 11 cu ft of gas at 2000°F. A description of the design and operation of a pilot plant for flash drying coal dusts is presented. This plant dries 1/16 in. by 0 coal dust in suspension in 1.5 to 2 sec with 600°F gas at a rate of 1300 lb per hour per square foot of column area and operates continuously at an efficiency of about 85 pct. The design and operation of another pilot plant for drying 1/8 in. by 0 coal dusts Is also described. This unit dries coal in the fluidized state using the sensible heat of gases introduced at 2000°F and processes coal at a rate of about 1500 Ib per hour per square foot of grate area at 85 to 90 pct efficiency. Over 90 pct of the bed moisture of low-rank coal dusts can be removed by the methods described. The heating value of lignite can be increased 45 pet and that if subbituminous coal 25 pct in a few seconds. The physical and chemical properties of coal dusts before and after drying are presented in the report, and it is shown that the bulk density of the dried coal is equal to that of the raw coal. This phenomenon makes it possible to ship 25 to 45 pct more heat in a railroad car with consequent savings in freight costs. Introduction For several years the Subbituminous Coal and Lignite Section of the Coal Branch of the Bureau of Mines at Golden, Colo., has been concerned with upgrading low-rank coals by removal of natural bed moisture. These fuels contain 10 to 50 pct total moisture, which reduces their industrial value considerably. In 1938, investigations were initiated in cooperation with the University of North Dakota to study drying of lignite by the Fleissner process with heat derived from high-pressure saturated steam. Two pilot plants were built, and two reports were published giving the results of this work.l,2 It was demonstrated that lump lignite and subbituminous coal

Jan 1, 1950

By D. R. Spink

In the preparation of zirconium and hafnium metals, there are many indications that impurity levels control the physical and chemical properties of the metal. The purpose of this work was to develop methods of producing pure raw materials that could be reduced to highly pure metals. Early work by the Carbomcndum Metals Co. and others indicated that certain fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. We have developed workable fused salts along with a continuous and higly efficient scrubber design which can be used to produce very pure zirconium tetrachloride. Metal made from the purified tetrachloride has been shown to approach crystal bar metal in purity. Scrubber designs are discussed with recommended materials of construction. VARIOUS methods have been used to purify zirconium (and hafnium) tetrachloride. Most of these methods involve thermal degassing initially (the removal of more volatile compounds at temperatures below that where zirconium tetrachloride exhibits a significant vapor pressure) followed by a sublimation step (which conveniently leaves the nonvolatiles behind.) While these procedures effect definite purification, such processing is batchwise and does not result in optimum purification. Early work by The Carborundum Metals Co. and others indicated that fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. The objective of this work was to develop a continuous fused-salt scrubbing process that would yield high-purity zirconium and hafnium tetrachlorides. The term "fused salt" refers to the molten state of ionic compounds and as used here, specifically refers to alkali metal and alkaline earth halides. Fused salts, because of their many valuable properties, are becoming increasingly im- portant industrially. These valuable properties of the fused salts are: 1) stability at elevated temperatures; 2)low vapor pressure; 3) low viscosity; 4) ability to dissolve many different materials; and 5) good elctctrical conductivity. All but the last property enhances the use of fused salts as scrubbing agents for zirconium and hafnium tetrachlorides. Fused-salt scrubbing may be defined for our purpose as the intimate contact between a gaseous compound and a molten salt with the purpose of removing impurities from the gaseous compound. In this case, the gaseous compound is zirconium tetrachloride which submlimes at 331°C. When this gas is contacted with a molten salt, impurities such as aluminum, iron, and titanium are removed and the resulting product is considered fused-salt scrubbed. Zirconium and hafnium are sold to a purity specification. Generally speaking, normal production without scrubbing is capable of meeting specifications. There are, however, several considerations That make the knowledge of methods of additional purification highly desirable. These are: 1) the control of product analysis; 2) the production of a pure product for special applications; 3) the salvaging of off-specification material; and 4) the use of raw materials with higher impurity levels than 1 he present raw materials. You will note that items 1 and 2 are somewhat complementary to each other and that item 4 assumes that The present process has impurity removal limitations. To better understand the part that fused-salt scrubbing of zirconium tetrachloride plays in the manufacture of zirconium, Fig. 1 contains an illustrated flow sheet of the industrial production of zirconium metal. In referring to Fig. 1, we can point out the specific benefits derived from our ability to purify zirconium tetrachloride. Purification of the crude (hafnium-containing) zirconium

Jan 1, 1962

By J. B. Clark, A. S. Yue

PfANN1 has shown that when a cylinder of molten binary alloy freezes directionally, the solute distribution can be described analytically by cg=k(l-g)k-1 [1] in which Cg is the solute concentration in the solid at the point where a fraction g of the original liquid has frozen and Co is the initial solute concentration. The term k is the effective distribution coefficient of the solute and is defined as the ratio Cx/CL where Cl is the solute concentration in the main body of the liquid. Both the slope and the intercept at -log (1 - g) = 0 of a logarithmic plot of Eq. [I.] provide a measure of k. Under conditions of freezing where diffusion in the solid is negligible and the solute concentration in the liquid is uniform, the effective distribution coefficient k, derived as above, is equal to the equilibrium distribution coefficient taken from the phase diagram. However, under ordinary freezing conditions, even though solid-state diffusion is negligible, the solute rejected from the freezing solid does not have sufficient time to diffuse uniformly throughout the main body of the liquid. A concentration gradient is formed in a boundary layer in front of the advancing solid-liquid interface as pointed out by Rutter and Chalmers.' Thus, under these conditions, the concentration of the freezing liquid in the boundary layer is higher than that predicted from the equilibrium phase diagram and consequently the effective distribution coefficient k, obtained from directional freezing experiments, is larger than the equilibrium distribution coefficient. The symbol k will designate the effective distribution coefficient in the discussion which follows. In this paper, the determination of the effective distribution coefficient is demonstrated for several dilute binary alloys and a polynary magnesium alloy. The effect of freezing rate on the value of the derived k is presented in detail. An example for the calculation of the solidus in a dilute binary solution using the experimentally determined effective distribution coefficient is given. MATERIALS STUDIED Binary magnesium alloys of copper, nickel, and zinc containing approximately 0.10 wt pct solute and a polynary alloy containing approximately 0.10 wt pct each of several elements were selected for study. The spectrographic analyses of these alloys are given in Table I. The analyses are believed accurate to within +5 pct of the stated value. EXPERIMENTAL PROCEDURE Extruded rods of the alloys, 3/8 in. in diam and 11 in. long were used for directional freezing studies. The alloy rods were melted horizontally in a high-purity graphite boat by a Nichrome-wound tube furnace which moved parallel to the length of the rod. The boat was supported inside a Vycor tube suitably connected to provide a protective atmosphere of dry SO2. For an experimental run, the following procedure was used. The alloy rod was cleaned in dilute HNO, and dried. The graphite boat containing the alloy rod was placed within the Vycor tube and the tube connected to the gas train' The 'ystem was purged for 20 min with dry argon and then a flow of dried SO, was maintained for the duration of the run. The movable furnace was positioned and either all or a desired portion of the alloy rod was melted. After attainment of steady-state temperature gradients the molten bar was solidified from one end to the other at a controlled rate by pulling the furnace along the length of the bar at the desired speed. At the conclusion of the run, the directionally frozen alloy rod was analyzed spectrographically at 1 1/4-in. intervals.

Jan 1, 1961

By Paul F. Sikora, John W. Weeton, Philip A. Clarkin

Effects of variations in carbon content and micro-structure on the stress-rupture properties of a liquid-phase-sirztered, Izeut-resistunt alloy were studied. Using the powder rnetallurgy technique, specimens could be produced having stress-rupture profierties equivalent to or better than those of the alloy in wrought form. In addition, sintered specimens were easily hot worked even when carbon contents were as high as I pct. Correlations between stress-rupture properties and micro structure were obtained in some cases. IT is well known that many alloys used in high-temperature service are quite complex both from the standpoint of chemical composition and microstruc-ture. During the development of these alloys their complexity has in some cases led to treatment schedules which, while practical, often do not fully utilize available alloying elements. For example, in some alloys, massive carbides that form during ingot practice may never be dissolved by reasonable solution treatments and therefore are unavailable for subsequent precipitation hardening, Ref. 1. This investigation was undertaken to determine whether the powder metallurgy method of consolidation might provide distinct advantages over the conventional melting method. First, segregation of alloying elements might be eliminated or reduced and thus a more efficient use of these elements obtained. Second, the structures produced in powder specimens might differ considerably from those normally seen in castings, which would perhaps result in better response to subsequent mechanical or thermal treatments. If these results could be achieved, it was felt that both forgeability and stress-rupture properties might be improved. The alloy used in this investigation was S-816 produced by powder metallurgy methods. The influence of carbon content over the range of 0.1 to 1.0 wt pct was studied for the alloy in the as-sintered condition and after three additional treatments involving heat treatment, hot swaging, and combinations thereof. EXPERIMENTAL Standard S-816 has the composition shown in Table I. It is a cobalt-base alloy having a nominal carbon content of 0.4 pct and is classified as a precipitation-hardening alloy. This alloy was chosen because it is representative of a class of heat-resistant alloys and because adequate information was available concerning its response to various treatments and its subsequent properties. For this study, -100 mesh alloy powder having essentially the same composition as shown in Table I but without the 0.4 pct C was used. Desired carbon variations, achieved by wet mixing the alloy powder with graphite, ranged from 0.1 to 1.0 wt pct. Specimens were hydrostatically pressed and then sintered in vacuum by slowly heating until incipient melting was observed. Sintering this way gave a liquid phase in the interstices of the powder particles and achieved reasonably high densities. The average density of as-sintered specimens was about 95 pct of wrought alloy density. In order to obtain various microstructures, some specimens were heat treated (solution treated for 24 hr at 2150°F, water quenched; aged 16 hr at 1400°F, air cooled); others were hot swaged at 2150 o F (50 pct reduction in area), while still others were hot swaged (50 pct reduction in area) and then given the above heat treatment. During hot swaging it was observed that forgeability was quite good even when specimens contained as much as 1.0 pct C. Specimens were evaluated by stress-rupture test-

Jan 1, 1962

By W. A. Wood, H. L. Wain, R. I. Garrod

The mechanical behavior of recrystallized chromil~m of high purity has been studied, principally in torsion and to a lesser extent in tension, at temperatures between —196oand 350oC. Depending upon the conditions of test, the material may show brittle or ductile behavior or an intermediate or subduc-tile state having some of the characteristics of each. This latter state existed at temperatures between approximately ±50°C and was characterized by a) extensive creep at stresses well below the normal fracture stress, b) nonelastic loading/unloading effects during creep, c) strain softening under cyclic loading, and d) final failure of a brittle type. Suggestions are made on the dislocation processes and interactions which give rise to subductile behavior The ductile-brittle transition in bee metals has been studied mainly by tension and bend tests. These methods, however, favor crack propagation which may follow too closely on initiation for detailed study of the transition itself. For work of this nature, therefore, other modes of deformation less favorable to crack propagation may be preferable. This paper describes a study of the ductile-brittle transition in chromium which is based mainly on torsional testing although a few subsidiary experiments were made in tension. It appears to reveal at the transition an intermediate state that cannot properly be described as either brittle or ductile. Torsional tests on chromium have been made by other workers1 but not, as here, primarily for study of this intermediate state. EXPERIMENTAL The chromium, in the form of swaged rod, was prepared by techniques already described.' The particular material used was one in which the main impurities were 0.03 wt pet 0 and 0.006 wt pet N and one in which transition from ductile to brittle states in torsion conveniently fell at about room temperature. For torsion, test specimens were from 5/16-in.-diam rod to provide test portions 1-1/4 in. long by 7/32 in. diam, a twist of 1 deg thereby corresponding throughout this paper to 0.0015 surface shear. The specimens before test were annealed for 2 hr at 1200°C in vacuo, which left them with a re-crystallized grain size of about 0.01 mm, and then electropolished. They were tested under dead-weight loading in an apparatus in which they could be surrounded by a furnace or cooling chamber, tests in practice being made at various temperatures between -196" and +350°C. For tension tests, cylindrical specimens were prepared in a similar manner and tested at room temperature under dead-weight loading. RESULTS (TORSION) Subductile State. The state described above as intermediate between brittle and ductile may be perhaps best defined by reference to torque/twist curves at various temperatures. These are grouped in Fig. 1. Below about -50°C the material was brittle, in the sense that it exhibited little plastic deformation under stress and fractured by cleavage along planes of maximum resolved tension, which in torsion produces the well-known helical type of fracture. The deformation is typified by the curves for -196" and -150°C in Fig. 1; it shows a slight but progressive deviation from linearity above a certain torque, here about 50 lb-in., until fracture occurs at about 95 lb-in. A feature to which it is desired specially to call attention is that under none of the loads did the specimens show significant creep.

Jan 1, 1964

By W. W. Krysko

In order to calculate the critical particle size of lead oxide entrapped in lead, Stoke's Formula may be applied. All data were available except figures for the density of lead oxide at elevated temperatwes. The density of lead oxide was determined by means of dilatometmetrc and volumetric methods up to 1010°C. Graphs of the density of lead and lead oxide as well as the viscosity of lead are given and discussed, with the conclusion that the most unfavorable region for the separation of lead oxide from molten lead lies just above the melting point of lead. DURING previous investigations, particularly on the dedrossing of lead with aluminum1 and the oxygen solubility in lead,' the critical particle size of lead oxide which could be entrapped in solidifying lead was estimated by calculation, and it was shown that high values found for the oxygen content of lead may be due to the method of sampling and the entrapped particles of dross. Unfortunately, due to lack of data, an exact mathematical solution was not possible. The particle size which will separate under a given condition can be estimated from Stoke's Law, which states that where: d = diameter of the critical particle size ¦q = viscosity of lead in Poise V = constant velocity in cm sec-I g = 981 cm sec-2 61= specific gravity of lead 62= specific gravity of lead oxide The depth of the lead bath and the time before solidifying define the velocity. The viscosity of molten lead is known from earlier work by Krysko and is given in Table I. The specific gravity of lead is also known, see Table II. These values are according to Hofmann. A careful survey of literature revealed no values for the density of lead oxide at elevated temperatures. The present investigation was therefore conducted to provide this information. RESEARCH INVESTIGATIONS The density of lead oxide was determined from the following experiments: 1) Determination of the density of lead oxide at room temperature. 2) Dilatometric investigations on the same samples. 3) Determination of the shrinkage at the liquid-solid trans£ormation. 4) Density determinations on liquid lead oxide. 5) Time temperature curves during cooling. 1) The samples for the determination of the density of lead oxide in the solid state were prepared in the following manner. Molten lead oxide was cast into I hot mold which could be opened along the longitudinal (vertical) axis. The cast samples were cylinders of approximately 10 mm diam and approximately 80 mm length. The cylindrical hot mold was open at both ends and was placed on a large copper chill plate shortly before casting. The solidification of the lead oxides proceeded upwards without any formation of internal cavities. The sample was carefully checked with respect to density and crystalline appearance, and only the lower portions which were crystalline and free from porosity were used. The density was determined in a specially made pyknometer-like container, where the surplus liquid was squeezed out through an orifice approximately 1/10 mm in diameter. Mercury or water was used as the liquid. The densities of the samples were calculated from the weight, volume, and mean specific gravity of eight samples was 9.62 * 0.05 g cm"3 at 22"~. 2) The samples were machined to approximately 1 1/2 in. in length and fitted into a dilatometer. A

Jan 1, 1962

By J. P. Heller

The purpose of this discussion is to comment briefly on one of the points raised in the paper. The topic is that referred to in the Conclusion 2, in which the authors note a "disproportionate increase in mixing rate" as they proceed from a displacement performed at viscosity ratio 0.998 to one at 1.002. The recovery curve of this displacement, Fig.2A, shows a quite noticeable difference between the two runs in which displaced and displacing liquids were interchanged. This difference is ascribed by the authors to the change in viscosity ratio between the two experiments. This interpretation of the experimental results must certainly be based on rather precise measurements of the fluid viscosities or, at least, of the ratio of their viscosities. The ordinary Ostwald viscometer, employed in the usual way, is only just able to distinguish between liquids whose viscosities differ by two or three parts per thousand. The experimental refinements which then must have been necessary to measure with any precision a viscosity ratio of 1.002 would be worthy of mention. Indeed, one would have expected the authors to devote at least a paragraph to the display of this technique. For the same reason - to emphasize that the details of such unusually critical experimental work should be reported and discussed in the literature — I would have liked to see some comment by the authors on the requirements for temperature control during both the viscosity measurements and the displacement experiments. The temperature coefficient of viscosity of Soltrol C at room temperature has been measured in this laboratory at about - 1.9%/1°C. How much did the coefficients for the fluid mixtures used in the experiment differ from this and from each other Even if the two fluids were identical in this respect, it would appear that a temperature difference of .l°C between them in the flow system would produce a viscosity con- trast equal to that imposed by their composition. Reference to the experimental solutions of these problems would render Conclusion 2 more credible. Published theoretical work on the stability problem contains no indication of such extreme sensitivity to the viscosity ratio in the immediate neighborhood of unity. On the contrary, perturbation calculations such as those made by Chuoke1 and Perrine2 lead to initial finger growth rates proportional to the first power of the viscosity difference. The later instability growth calculated by Scheidegger,3 using the assumption of zero pressure gradient perpendicular to the average flow, is also simply proportional to the viscosity difference. The conflict regarding the sensitivity of the dependence of instability growth or mixing rate on the viscosity contrast needs explicit recognition in the literature. In particular, it would seem that the experimental work reported here should be supported by a more detailed description of the viscosity controls. Further discussion of possible alternative interpretations of the data would also be in order. For instance, is it possible that the unconsolidstted bead pack used changed its characteristics between the runs (due, perhaps, to the handling and inverting involved in the injection of the front) Or, are the data points of Fig. 2A averages from several runs performed in a series in which the two liquids alternated as displaced and displacing fluids? To summarize, it seems to me that the relationship asserted by Conclusion 2 in the paper needs the support of more detailed experimental evidence. REFERENCES 1. Chouke, R. L., van Mews, P. and van der Poel, C.: "The Instability of Slow Immiscible Viscous Liquid-Liquid Displacements in Porous Media", Trans., AIME (1959) Vol. 216, 188.

By Joshua Pelleg, G. M. Lindberg

THERE are three reported investigations of self-diffusion in niobium. Lundy et al.1 found their self-diffusion data well represented by the equation

Jan 1, 1970

Manuscripts of Papers for Presentation at Arizona Meeting, Sept. 18 to 23, 1916, must be in hands of Secretary by July 1, 1916.

Jan 5, 1916

By Louis Huber

THE Liberty tunnels extend through a very steep hill in Pittsburgh (locally called Mount Washington) for a distance of slightly over a mile. The two tunnels parallel each other and are 59 ft. apart, center to center (Fig. 1). They are for vehicular traffic, and in each there is ample space for two lines of vehicles. Northbound traffic, towards downtown Pitts- FIG. 1.-NORTH PORTAL OF LIBERTY TUNNELS. NOTE THE WINDBREAK AT END OF EAST TUNNEL. burgh, is confined to the east tunnel and southbound traffic to the west tunnel. The South Hills residential district is separated from downtown Pittsburgh by Mount Washington, a steeply rising escarpment south of and adjacent to the Monongahela River. The Mount Washington district immediately south of the Monongahela River has been reached, for many

Jan 1, 1927

By F. R. Hensel

THE alloy under discussion is a nickel-silicon bronze and is one of many age-hardening or precipitation-hardening FIG. I.-EFFECT OF QUENCHING AND AGING TEMPERATURES ON HARDNESS OF TWO TYPICAL NICKEL-SILICON BRONZES, NO. 2351 AND No. 2362. copper-base alloys. The hardening con-stituent is a nickel-silicon compound.1 The quenching temperature necessary to pro-duce hardening by a subsequent aging treatment is a function of the composition and extends from about 700'C. to ()50'C.; the aging temperature range extends from 400° to 600°C. The work carried out by the authors of this paper was confined to cast alloys having compositions within the ranges of 1.5 to 3.00 per cent Ni; 0.4 to 0.75 per cent Si; balance, copper.

Jan 1, 1940

By Sheldon P. Wimpfen, Nelson Severinghaus

13.2-1. Introduction. Man's first association with industrial minerals came at the dawn of history when a remote ancestor first put a few rocks together to protect a fire or selected colored clays to decorate his face. He was dealing with industrial minerals when he selected flint to tip his arrows or scrape a hide. From that inauspicious beginning shrouded in the mists of man's earliest history, industrial minerals have grown tremendously in importance to our civilization. The growth rate of the industrial minerals, or nonmetallic group, has been considerably greater than that of the metals group, as can be seen by the following Fig. 13.2-1: [ ] Industrial minerals produced in the five-year period of 1961-1965 had more than twice the dollar value of the metals produced:

Jan 1, 1968

By J. J. Mike

During the past few years the combination of continuous billet casting with in-line reduction has been studied and several machines have been built with this capability included in the design parameters. (1,2,3,4,5) In-line reduction and continuous casting in combination are obvious and attractive. As pinch rolls are already in place for the continuous casting operation, it can be readily seen that a redesign of the mechanical and electrical equipment of the pinch rolls is all that is necessary to have in-line rolling. There have been numerous in-line reduction experiments conducted by simply increasing the pinch roll pressure on existing machines. (6,7,8,9) These generally failed to produce quality billets and often resulted in internal metallurgical defects (Figure 1).

Jan 1, 1972

By Werner Joseph, Richard R. Knobler

When the first batch of refined copper ingots was cast at Mantos Blancos in January 1961, eight years of exploration, development and metallurgical pioneering by Mauricio Hochschild & Co. had come to a successful conclusion. This Chilean copper deposit, located in the Atacama Desert 30 miles from Antofagasta, is now producing approximately 20,000 tons of copper per year. The Mantos Blancos deposit has been known since 1912 and various attempts had been made to work the high-grade zones before the present operation was started. The major drawback of the ore to any previous development was its chloride content which varies between 0.4% and 1.5% C1. Although the chloride ruled out the conventional leaching-electrolysis scheme, it did lend itself to the process of precipitating the copper as cuprous chloride.

Jan 1, 1962

By Eugene A. Stephenson

In November, 1932, Dr. Lacey, of the California Institute of Technology, presented before the American Petroleum Institute some of the results of his research under Project 371. The investigations described dealt particularly with changes in the physical properties of petroleum that result from the solution of natural gas therein. The solubility of Santa Fe Springs dry gas, containing 87 per cent methane, 8 per cent ethane and 5 per cent propane, had been determined in various crudes at 100' F., and 2000 lb. pressure per square inch as shown in Table 1 and Fig. 1 herewith. Originally the computations were made in terms of cubic feet per barrel, but' for a more uniform basis of comparison the results are also shown as cubic feet of gas2 per cubic foot of oil.

Jan 1, 1935

By Stephen E. Erickson, Donald G. Oss

The need for instrumentation and automatic control of the various parameters in the heavy media process of iron ore beneficiation has been apparent for some time. Continued demands for higher grade, competitive products from the Mesabi Range have made it necessary to increase the efficiency of the process in every possible way. In a typical heavy media flow scheme for iron ore beneficiation (Fig. 1) a sized, prepared feed (generally about minus 1 ¼ in. to plus ¼ in.) is fed to a heavy media separatory vessel, along with a ferrosilicon slurry. A separation of the feed is made on the basis of specific gravity. Low density particles overflow a tailings discharge weir, while high density ore particles sink to the bottom of the high density pool and are moved away to the concentrate discharge chute.

Jan 5, 1962