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By D. Mills, G. B. Craig

ZIRCONIUM has been float-zone-refined in an electron-beam furnace and the redistribution of oxygen, iron, and tungsten has been measured. The iodide zirconium used in the present experiments initially contained both oxygen and iron in the range 100 to 200 ppm by weight, and tungsten in amounts less than 10 ppm. Float-zone refining of zirconium, using induction heating, has previously been attempted by Kneip and Betterton1 and Langeron.2 Kneip and Betterton were primarily interested in the removal of iron and nickel. They achieved some purification, with respect to both these elements, in material given up to six passes at 150 mm per hr under an argon atmosphere. Langeron reported purification for a large number of elements after four completed passes in a static vacuum system operating at pressures less than 10-6 mm of Hg and with rates of zone travel between 30 and 40 mm per hr. He did not report oxygen concentrations, but stated that there was inverse segregation of this element. westlake5 has also used a minimum of four zone passes to remove iron from zirconium. No rates or conditions were given. Belk6 has shown that tungsten contamination can occur during electron-beam melting. He reported an increase from 0.01 to 0.05 pct by weight tungsten in molybdenum after four complete zone passes. The vacuum system for the electron-beam unit used in the present investigation consisted of a single-stage rotary pump backing a liquid-air-trapped oil-diffusion pump. A pressure of less than 10-8 mm of Hg was obtained with Dow-Corning 705 fluid in the diffusion pump. In order to avoid contamination of the zirconium by evaporation from the tungsten filament, a special focusing cage4 was employed. Three rates of zone travel, 114, 38, and 4 mm per hr, were investigated, with the liquid zone moving from the bottom to the top of the bar. The bars used were 3 mm diam and the total melted length was 130 mm. Oxygen was analyzed by neutron-activation analysis using a neutron flux of 10' neutrons per sq cm per sec to form the isotope N16 by the 016 (n,p) N16 reaction. The standard deviation is quoted for each oxygen determination. The iron and tungsten analyses were performed spectrographically, and the precision is estimated to be ±6 pct. Analyses for tungsten were all below the detectable limit of 10 ppm, confirming the protection given by the focusing cage. No significant redistribution of oxygen was found at the two higher rates of zone travel. The redistribution of oxygen and iron obtained after five passes at a rate of zone travel of 4 mm per hr (1.1 x 10-4 cm per sec) is recorded in Tables I and 11. Burris, Stockman, and Dillon3 have estimated the distribution of solutes during multipass zone refining. Using their curves for an effective distribution coefficient of Keff = 1.5 and 2 for oxygen and Keff = 0.3 for iron, the expected concentrations were estimated for the present material. These are shown in Tables I and 11, along with the experimentally measured values. The calculated concentrations are based on a molten-zone length of 10 pct of the total melted length, whereas in the present experiments the molten zone was approximately 5 pct of the total melted length. The effect of zone length on solute redistribution is most pronounced after a large number of zone passes. Comparison with Pfann's published data8 for solute redistribution for various Keff's and zone lengths indicates only small differences at low numbers of completed zone passes. It is evident that the expected distribution has not been realized in the case of iron. Scrapings of material deposited on the inner surfaces of the electron-focusing cage were found to be magnetic. It is, therefore, concluded that redistribution of iron is masked by evaporation. Deposition of iron inside the focusing cage was observed at all rates of zone travel. The results of the investigation may be summarized as follows: 1) Segregation of oxygen is typical for a solute with a distribution coefficient, Keff > 1. 2) No redistribution of oxygen takes place at high rates of zone travel. 3) The distribution coefficient for oxygen lies between 1.5 and 2.0. 4) Purification with respect to iron occurs mainly by evaporation. 5) The focusing cage is effective in preventing tungsten contamination.

Jan 1, 1967

By D. M. Waldorf

Steam permeability measurements have been made in the laboratory on several samples of natural reservoir materials. The steam temperatures and pressures were selected to simulate conditions which might exist in a reservoir during the injection of steam. For each sample tested, the experimental permeability to superheated steam was comparable to that measured with air and no evidence of plugging was detected. Some samples were exposed to water at various temperatures and plugging was found to occur in materials which contained significant quantities of monmorillonite clay. Temperature had little effect on the degree of plug-ning between 75 and 325 F. The measured pemeabilities tended to increase slightly with temperature, but the changes were small compared with the initial loss of per~neability on wetting. Sequential pemzeability measurements were made on two samples using air, water, steam, water and air, in that order. Both samples were water-sensitive and plugged extensively after the initial injection of water. Upon exposure to superheated steatm the samples dehydrated and their permenbilities to superheated steam were comparable to those initially measured with air. The remaining measuretnetzts with water and air confirmed that the water plugging was reversible and that the samples were not seriorrsly damaged during the tests. INTRODUCTION The swelling of water-sensitive clays during water floods has long been recognized as a potential source of reservoir damage. The recent extensive application of steam injection and stimulation has compounded this problem since both hot water and steam (as well as fresh water at reservoir temperatures) are, at sume time, in contact with the producing zone adjacent to the bore of a steam injection well. The purpose of this paper is to present data which compare the sensitivity of some natural sedimentary rock samples to water at various temperatures, and to super-heated steam. Some properties of montmorillonite clay are briefly reviewed, and comparisons are drawn between empirical data and the predicted behavior of the montmorillonite known to be present in the samples. PROPERTIES OF MONTMORILLONIT E CLAY Water initially adsorbs on dry N a -montmorillonite clay in discrete layers in the interlaminar space between clal platelets. The platelet spacing, which is 9.6 A (angstroms) for a dehydrated clay, has been observed to expand in discrete steps to 12.4, 15.5, 18.4 and 21.4 A spacings, indicating the formation of four discrete layers of regularly oriented water molecules.' The first two layers are easily formed by hydrating a dry sample to equilibrium in an atmosphere with carefully controlled humidity. The formation of the higher layers is more difficult. The usual X-ray diffraction patterns of the more highly hydrated samples indicate a gradual increase in the average spacing betwcen 15.5 and 19.2 A, followed by a discontinuous expansion to 31 A when the weight ratio of water to dry clay is between 0.5 and 1.2.' Platelet expansion above 31 A proceeds monotonically as the moisture is increased and no regular arrangement of the platelets ib observed. Water-sensitivity in sedimentary rocks is usually associated with Na-montmorillonite clay when it is in the noncrystal-line state. Mering3 found that the average lattice spacing of sodium montmorillonite hydrated at 68 F and 70 per cent relative humidity was 15.5 A, and that the spacing, at 92 per cent humidity was 16.5 A. The water adsorbed at the higher humidity has the same free energy as liquid water at 65.6 F. Kolaian and Low' used a tensiometer to measure the thermodynamic properties of water in diffuse suspensions of montmorillonite clays relative to pure water. They observed that water in suspensions as dilute as 6 per cent clay became partially oriented when left undisturbed. The bonding associated with this orientation was not extensive because the free energy difference between the water in suspension and pure water was only a few millicalories per mole. They also found that the measured free energy difference decreased rapidly with temperature and became negligible above 100 F. This evidence indicates that montmorillonites contained in sedimentary rocks would dehydrate to a crystalline structure when exposed to superheated steam, and that the rock permeability measured with steam would be equivalent to that measured with air. The effect of elevated temperatures on the swelline of montmorillonite clays in aqueous suspensions has not been investigated. The Gouy-Chapman diffuse-ion-layer theory has been used to predict the swelling pressure of clay suspensions in dilute salt solutions at room temperature with reasonable success. theory also correctly predicts the direction of the thermal response of Na-mont-morillonite swelling pressures in dilute salt suspensions, 9 Over the temperature range of 33 to 68 F, an increase in

Jan 1, 1966

By AIME AIME

THE CHAIRMAN of the fast growing Petroleum Division is not only a graduate of the University of California, but a third generation native son. After a few years spent in hard-rock geology, his professional efforts were transferred to the sedimentaries and to petroleum investigations, as a consulting geologist. For ten years these investigations covered the Rocky Mountain, Oklahoma, Texas, and eastern districts. After the war he returned to Casper, Wyo., as chief geologist for the Consolidated Royalty Oil and Western Exploration Companies. This employment afforded him the opportunity to study particularly the economic relationship between the lessor-lessee interests in development and production, a somewhat unusual type of petroleum specialization.

Jan 1, 1939

By H. O. McLeod, J. M. Campbell

This paper presents the results of the data obtained in the first stage of a long-range study at high pressures of the system, vapor-hydrate-water rich liquid-hydrocarbon rich liquid. The data presented are for the three-phase systems in which no hydrocarbon liquid exists. Tests were performed on 10 gases at pressures from 1,000 to 10,000 psia. One of these was substantially pure methane, and the remainder were binary mixtures of methane with ethane, propane, iso-butane and normal butane. Several conclusions may be drawn from the data. 1. Contrary to previous extrapolations, the hydrocarbon mixtures tested form straight lines in the range of 6,000 to 10,000 psia which are parallel to the curves for pure methane, when the log of pressure is plotted vs hydrate formation temperature. 2. The hydrate formation temperature may be predicted accurately at pressures from 6,000 to 10,000 psia by using a modified form of the Clapeyron equation. The total hydrate curve may be predicted by using the vapor-solid equilibrium constants of Carson and Katz' to 4,000 psia and joining the two segments with a smooth continuous curve between 4,000 and 6,000 psia. 3. The use of gas specific gravity as a parameter in hydrate correlations is unsatisfactory at elevated pressures. 4. The hydrate crystal lattice is pressure sensitive at elevated pressures. INTRODUCTION Prior to 1950 many studies had been made of the hydrate forming conditions for typical natural gases to pressures of 4,000 psia.""'"'"" Most of these attempted to correlate the log of system pressure vs hydrate formation temperature, with gas specific gravity as a parameter. One of the more promising correlations was made by Katz, et al, which utilized vapor-solid equilibrium constants. The only published data above 4,000 psia are those of Kobayashi and Katz7 for pure methane to a pressure of 11,240 psia. In the intervening years, most published charts for the high-pressure range have represented nothing more than extrapolations of the low-pressure data, with the methane line serving as a general guide. The reliability of these charts has become increasingly doubtful (and critical) in our present technology as we handle more high-pressure systems. The portion of our high-pressure hydrate research program reported here was designed to: (1) investigate the reliability of existing charts; (2) obtain actual data on gas mixtures to 10,000 psia; and (3.) develop a simple hydrate correlation that was more reliable than those which simply used specific gravity as a parameter. Binary mixtures of methane and ethane, propane normal butane, or iso-butane were injected into a high-pressure visual cell containing an excess of distilled water. Hydrates were formed and then melted to observe the decomposition temperature of the hydrates at pressures from 1,000 to 10,000 psia. EQUIPMENT The equipment consisted of a Jerguson 10,000-lb high-pressure visual cell, a 10,000-1b high-pressure blind cell and a Ruska 25,000-1b pressure mercury pump. The visual cell was placed in a constant-temperature water bath controlled by a refrigeration unit and an electric filament heater. A Beckman GC-2 gas chromatograph was used in analyzing the gas mixtures after each run was completed. EXPERIMENTAL PROCEDURE After evacuating the gas system, the heavier hydrocarbon was injected into the high-pressure mixing cell to that pressure necessary to give the desired composition. This cell then was pressured to 1,100 to 1,200 psia by methane from a high-pressure cylinder. The mixing cell holding the gas contained a steel flapper plate and was shaken intermittently over a period of 15 minutes. After mixing, the valve to the high-pressure visual cell containing excess distilled water was opened, and the gas mixture was allowed to flow into the cell. The temperature in the water bath was lowered 10" to 15'F below the estimated hydrate decomposition point. As a first check, the temperature was increased at a rate of 1°F every six minutes to find the approximate point of decomposition. It was again lowered 1.5° to 5°F to form hydrates. The temperature was raised to within l° of the estimated decomposition point and then increased 0.2F every 10 to 15 minutes until the hydrates decomposed. This procedure was repeated at various pressures to obtain 7 to 13 points for each mixture between 1,000 and 10,000 psia. After completion of the hydrate decomposition tests, the gas mixture composition was analyzed with a calibrated gas chromatograph. These gas analyses have an estimated error of ± .1 per cent.

By H. Udin

G. KUCZYNSKI* and B. H. ALEXANDER*—This paper represents a most noteworthy attempt to evaluate experimentally the surface tension of a solid metal. Because of the great importance of such measurements, any proposed method should receive the closest scrutiny before the results can be considered reliable. In regard to the experimental method, we think that the marking of the gauge length by means of tieing knots in the wire may be the cause of some of the spread in the results. Such a knot may be expected to tighten slightly, and thus increase the gauge length, when placed under stress at high temperature. Although this effect would be very small, amounting at most to only a few times the wire diameter. A fairly tight knot in a wire will decrease the wire length by about ten times the wire diameter, thus only a slight tightening of the knot would cause considerable spread in the results. Upon plotting the stress strain curves from the authors' data, the writers found that there was a fairly consistent tendency towards an S-shaped curve, instead of a straight line. Such an effect could be caused by the tightening of the knots. The writers think, however, that the experimental results are fairly reliable, but that there may be other methods of interpreting them depending upon what mechanism is assumed to be responsible for the shrinkage of the wires. The authors have assumed that the stress due to surface tension results in viscous flow. It should be made clear that it has never been demonstrated that viscous flow can occur in metal crystals even at very high temperatures. The experiments of Chalmers13 on tin, which are so frequently quoted as giving evidence of viscous flow at low stresses are by no means satisfactory. In his experiments, Chalmers found that only the initial rate of flow was approximately proportional to stress. He also found that the rate of flow varied markedly with time which, in his experiments, was less than 2 hr. Inasmuch as there is no proof of viscous flow in metals, and the authors have brought forth no conclusive evidence on this point, it may be worth while to investigate other possible mechanisms of material transport which would account for the shrinkage of the wires. The writers wish to point out that in these experiments the shrinkage of the wires can be adequately explained, according to a self diffusion mechanism. Thus, if we assume a concentration gradient for self diffusion which is a function of the radius of curvature of the wires, and assume that diffusion will occur so that the total surface area is decreased, we find the following expression for the self diffusion coefficient: where k = Boltzmann constant r0 = initial radius of the wire T = absolute temperature ? = surface energy 8 = interatomic spacing t = time e = strain at zero applied stress Eq 19 may be used to evaluate the self diffusion coefficient of copper, using the strain measurements obtained by the authors for zero stress as obtained by extrapolating their curves for 5 rail wires. By inserting a reasonable value for the surface energy (1500 ergs per cm2) we find: -66,000 D = 5 X 10e RT [20] The activation energy is of the correct order of magnitude, but the frequency coefficient is much too high, indicating that surface diffusion may be playing an important role. This discrepancy in the action constant is much smaller than the corresponding discrepancy obtained by the authors for the viscosity coefficient. The writers by no means propose that this proves that the shrinkage of the wires is due to self diffusion but we merely wish to point out that there are explanations other than that given by the authors. In this, as in any kinetic phenomena, it is necessary to study the rate of the process before anything can be said about the mechanism. The determination of surface tension given by the authors is based upon an interpretation of the data which embody the concept of viscous flow. The final proof of this concept will be obtained only after the time relationships confirming the authors' Eq 15 have been conclusively established. The rough linearity of the stress strain curves obtained by the authors for experiments run the same length of time should not be considered as proving that viscous flow is occurring. H. UDIN (authors' reply)—All of the test specimens were annealed at 1000°C for an hour or more before preliminary measurements were made. During this anneal the wires recrystallize, and the greatest part of grain growth takes place. Also, the knots sinter at the cross-over points. This does not in itself eliminate the possibility of end errors, although it greatly decreases their probable magnitude. It is still possible that some extension occurs due to creep in shear at the sintered points. If so, this effect would be quite independent of and superimposed on the normal shrinkage or extension of the wire itself. Within the precision of the experimental results, straight lines satisfy the data as well as do any other simple curves. Until data of greater precision are obtained, it is futile to discuss any possible trends away from linearity. The disagreement between Kuczynski and Alexander's Eq 19 and our Eq 18 is one of semantics and mathematics, not mechanism of flow, since Eq 18 is based on the self-diffusion concept of viscous flow. It would be interesting to learn how the mathematics leading to Eq 19 deviates from that of Eyring and of

Jan 1, 1950

By John D. Sullivan, Chester R. Austin, Edwin J. Rogers

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By John D. Sullivan, Edwin J. Rogers, Chester R. Austin

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By J. T. Michalak, H. W. Paxton

The recovery of the initial flow stress of poly-crystalline iron is characterized by a) a logarithmic time dependence; b) an increasing activation energy with increasing recovery; c) an increased ?,ate and fraction of recovery with decreased temperature of deformation; and d) an increased rate with increased deformation. Isochro)ml studies of the recovery of single crystals revealed more sluggish recovery. The original flou3 stress of single crystals could be regained by recovery anneals at 800"or 900°C. ThE great majority of the theoretical treatments and experimental studies of strain-hardening have been concerned with the close-packed lattices.' Very little effort has been expended on the bcc structure so that the theory of work-hardening of this lattice is essentially nonexistent. The limited amount of experimental data resulting from the direct studies on silicon-iron,2 low-carbon steel,3 and purified irons4"7 does not as yet permit a detailed analysis of the strain-hardening. Studies concerned with the effects of annealing following deformation have been few in number," have been somewhat limited in extent, and have had the disadvantage of using irons containing a substantial impurity content. The present research was undertaken to augment the limited knowledge we have of the characteristics of a bcc metal as regards strain-hardening and recovery from the strain-hardened state. The recovery of the flow stress has been employed since it was felt that the stress associated with the hardened state gives at least a fair qualitative description of the state of the imperfections causing the hardening. The study was concerned primarily with the recovery of flow stress following strain-hardening of polycrys-talline, zone-melted iron as a function of the amount of deformation, the temperature of deformation, and the time and temperature of the recovery anneal. A limited investigation of the recovery of the initial flow stress of single crystals of this same material as a function of the recovery temperature was also conducted in conjunction with the Lambot X-ray technique." MATERIAL The zone-melted iron used in this investigation was obtained through the courtesy of the American Iron and Steel Institute and Battelle Memorial Institute. The analysis, as given by the supplier indicated a maximum impurity content of 0.02 wt pct excluding those impurities listed in Table I. (The actual impurity content is very probably less than this since detection limits were considered as the amount of a particular impurity level.) Also listed in Table I are the interstitial impurity contents of the iron at various stages of experimental work indicating that these im-

Jan 1, 1962

By J. R. Low, M. Gensamer

During the course of an investigation into the drawability of automobile-body sheet steel, it became apparent that certain advantages would be possessed by a deep-drawing steel with a very low yield strength, but almost normal tensile strength, provided a reduction in yield strength could be accomplished without sacrifice of ductility and fine grain size. It would also be desirable to have this steel free from strainaging; that is, free from the tendency for the yield point to return after it had been eliminated by straining. It was known that wet hydrogen treatment acted to eliminate aging, but as carried out by other investigators, at relatively high temperatures, this treatment resulted in grain coarsening. It has been established by some of the experiments reported in this paper that all of these objectives can be accomplished by treatment in wet hydrogen at a low temperature, in the neighborhood of 720°C. The time of treatment is relatively short (about 3 hr. to completion with 20-gauge sheet) if the water content of the hydrogen atmosphere is made fairly high, say almost 30 per cent by volume. At this temperature, the grain size remains fine in the time required. After this treatment sheet reduced the usual amount by cold-rolling has a grain size of about A.S.T.M. No. 7. The yield point is completely eliminated, and the yield strength is reduced to a very low value, in the neighborhood of 15,000 lb. per sq. in. The stress-strain curve departs gradually from the straight-line elastic part after the fashion of nonferrous deep-drawing alloys. This elimination of the yield point is accompanied by a very low indentation hardness; for example, 32 Rockwell B or even lower. There is no aging as measured by increase in the yield strength upon aging at room temperature or for 3 hr. at 200°C., after stretching about 10 per cent in tension. Tensile strength is only slightly less than the box-annealed sheet, seldom dropping much below 40,000 lb. per sq. in. Elongation is practically unchanged, or increased slightly. The term yield point, as here used, refers to the phenomenon of heterogeneous deformation occurring at a substantially constant load, observed principally in annealed low-carbon steels. If such a steel is loaded in tension, the load increases steadily with elastic strain, suddenly falls, fluctuates slightly about some constant value for a time and then begins to rise again as deformation proceeds. The maximum initial load before the sudden drop is generally called the "upper yield point"; the value of the load where deformation proceeds at a

Jan 1, 1943

By E. I. Larsen, E. F. Swazy, F. R. Hensel

EXPERIENCE has indicated that hard bronzes are not suitable for bearing applications where high bearing loads and speeds are involved. It is the general practice to utilize softer materials for these purposes, such as copper, lead, silver, babbitt, lead-base alloys, and more recently aluminum-base alloys, preferably supported by a steel backing. It was the objective of the present investigation to study a new material produced by powder metallurgical methods susceptible to precipitation-hardening. TEST MATERIALS Preliminary tests were made with compacts containing copper, nickel and silicon in quantities sufficient to form 3 to 5 per cent nickel silicide. It was found that this type of alloy was susceptible to the formation of a soft surface shell when sintered in tank hydrogen. The depth of the shell depended on the length of sintering time and sintering temperature, and varied in thickness from a few thousandths to as much as one eighth inch. This soft shell resulted from the preferential oxidation of silicon, thereby reducing the efficiency of age-hardening by the nickel silicide compound. The body of the sintered compacts below the soft shell could be precipitation-hardened to a hardness of 70 to 85 Rockwell B, by quenching from. 900°C. and age-hardening at 450°C. A series of tests was made with various addition agents, in order to decrease the rate of preferential oxidation, and it was found that phosphorus was most beneficial in this respect. After considerable experimentation, the following nominal composition was accepted as standard: 2.4 per cent nickel; 0.8 silicon; 0.3 phosphorus; balance copper. The physical properties and certain bearing properties of this alloy are described in the present paper. PREPARATION OF COMPACTS Several methods of incorporating the hardening ingredient (nickel silicide) were studied. Compacts formed from copper, nickel and silicon powders were found to be inferior to those fabricated from prealloyed nickel silicide master alloys, because of the rapid oxidation of pure silicon during sintering. The use of a prealloyed nickel silicide hardener containing 25 per cent silicon and 75 per cent nickel could be further improved by preparing a master alloy, incorporating nickel, silicon, phosphorus and copper, having the following nominal composition: 25 per cent nickel; 7 silicon; 3 phosphorus; 64 copper. This alloy is brittle in. the cast condition and can be readily powdered. SINTERING PROCEDURE The blended powders were pressed at 25 to 40 tons per sq. in., the pressure depending on the size and shape of the compacts. Sintering was carried out in hydrogen or cracked ammonia atmospheres at

Jan 1, 1946

By John D. Sullivan, Edwin J. Rogers, Chester R. Austin

THE problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce light-weight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough so that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays[t] and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, particularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."2 The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. Commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the purpose of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By A. Cochardt, D. H. Feisel

HE success of the sintered aluminum powder material (SAP)' in raising the maximum useful temperature of aluminum alloys has stimulated effort in investigating similar systems in which the metallic matrixes have higher melting points. Examples of such systems which have been studied are nickel-alumina,2, 3copper-silica,4 copper-alumina,4 titanium-cerium oxide,5 and 80/20 nickel-chromium,8 cobalt,= and molybdenum7 matrixes with various hardeners. Conventional precipitation-hardened high-temperature alloys are often thermally unstable in service. The original fine particles that are responsible for good strength properties grow in size at elevated operating temperatures, a process termed "over-aging." This growth of precipitated particles causes a gradual loss in strength properties. A previous paperb describes the factors that govern the process of overaging, and estimates the time required for overaging of a nickel-alloy matrix dispersion-hardened by various precipitates such as are found in current high-temperature alloys, and by alumina. These calculations indicate that nickel-base alloys hardened with Ni3Al, Tic, or TiN are quite unstable at 1340" F (727°F). Such alloys should overage within a few hours at that temperature. A nickel-base alloy hardened with alumina, on the other hand, should behave differently. It should not overage appreciably within a thousand years. It was further shown8 that the thermal stability of the oxide-hardened alloy is mainly due to the low solubility of oxygen in equilibrium with alumina in the nickel-base matrix. Since the oxygen solubility is small, little oxygen can diffuse, and structural changes require very long times. This paper illustrates the effects of time and temperature on the structural stability of nickel alloy matrixes hardened by dispersions of Ni3A1, Ni3Ti, Tic, and alumina, and of nickel-chromium matrixes hardened by alumina. Hardness measurements and metallography have been used as a measure of structural stability. EXPERIMENTAL PROCEDURE Using the best information from published phase diagrams,'-l4 compositions of the Ni-Al, Ni-Ti, and Ni-Ti-C alloys were determined so as to have 5 vol pct of precipitate at 1350° F(732°C), the temperature selected to illustrate the effect of time on structural stability. Table I lists the chemical compositions of these alloys. Standard laboratory melting and alloying techniques were used in preparing ingots of the F-Series of alloys. The cast ingots, 1 3/4 in. in diam, were forged to 3/8-in. diam rods.

Jan 1, 1960

By Brison Robertson, W. P. Fishel

The carbide-forming tendencies of the various steel-alloying elements, or their affinities for carbon, is a subject that has received considerable attention, but little more than a probable arrangement of the elements as to their carbide-forming tendencies has been proposed. The physical properties of alloy steels depend upon the relative proportions of the elements present and their combinations. one important phase of this subject is the distribution of carbon between the various elements present. The distribution of car. bon between iron and other elements evidently sill depend upon: (I) the affinity of each for carbon; (2) the relative atomic masses of the elements present; and (3) the possible formation of compounds between the alloying and iron and between the elements themselves, In ternary steels the case is simplified, especially in systems in which the element and iron form no compounds, In such systems iron and the alloying element are competing for the carbon present. In this work the distribution of carbon between titanium and iron has been studied by measuring the relative amounts of iron carbide and titanium carbide present ill a series of annealed steels in which the ratio of titanium to carbon extended from 0.527 to 4.61. Ten Fe-Ti-C alloys, weighing about 250 grams each, were prepared by melting under a Vacuum, in an Induction furnace, Armco iron, carbon-free ferrotitanium (25 per cent Ti), and pure carbon. Vacuum melting prevented the formation of titanium oxides and nitrides, which would the the problem. The melts were made in graphite crucibles lined with sintered magnesium oxide. The ingots were the in the furnace under a vacuum and "'ere then completely annealed at 950°C. The determination of the amount of titanium carbide present was based upon the established insolubility of titanium carbide in boiling dilute (1:4) sulphuric acid, and the complete solubility Of free titanium and titanium-iron compounds in this acid. High-carbon ferrotitanium, which had been treated to remove free Ti and Fe. was found to be completely insoluble in the acid; and the carbon-free ferrotitanium used in making the alloys was found to be completely soluble. Others have reported the insolubility of titanium carbide in sulphuric and hydrochloric acids. Turnings from the ingots were digested with boiling sulphuric acid (1:4) until all action had ceased. The carbide residue was filtered off and analyzed for titanium, and in some cases for carbon. This represerifs the titanium that was united with carbon The filtrate from the carbide residue contains the portion Of the titanium that was in solid solution in the ferrite. Titanium

Jan 1, 1945

By R. I. Jaffee, H. R. Ogden, D. J. Maykuth, W. L. Finlay

Titanium with up to 7.5 pct Al forms single-phase a alloys that are work hardening, not heat treatable, and ductile as welded. The high aluminum Y phase alloys are not usefully ductile, despite their low hardness, but they have excellent oxidation resistance and hot hardness. LITTLE has been published on the effect of aluminum on the mechanical properties of titanium, despite the fact that two of the first four commercial alloys released by titanium alloy producers contained aluminum as an important alloying ingredient. These were both a-ß type alloys, one containing 4 pct A1 and 4 pct Mn and the other containing 3 pct A1 and 5 pct Cr. However, neither of these alloys reflects the true alloying nature of aluminum, since each contains important amounts of the ß-stabilizing addition, manganese or chromium. In a previous publication on the constitution of Ti-A1 alloys,' the authors showed that aluminum had a high solubility in a titanium and was strongly a stabilizing in nature. About 25 wt pct A1 is soluble in a titanium at room temperature. With as little as 5 pct added aluminum, the a transus temperature is increased from 882" to 970°C, and the correspond- ing ß transus to 995°C. The first intermediate phase in the Ti-A1 system is the ordered face-centered tetragonal TiAl phase, which extends from 34 to 46 wt pct Al. The present paper presents hardness data over the entire titanium-rich region of the system, through the TiAl phase, and mechanical property data on the alloy range capable of being fabricated. Methods of Investigation The materials used and general preparation of alloys, as well as experimental techniques used in the investigation of Ti-A1 alloys, have been adequately described.' Briefly, the preparation consisted of arc-melting the desired amount of high purity aluminum (99.99 pct purity) and iodide titanium (maximum hardness 100 Vickers, as deposited) together on a water-cooled copper hearth under a partial pressure of argon. The resulting button ingot was of such form that it could be fabricated without further treatment. All work was done using ingots weighing 10 to 15 g, which were hot-rolled to strip form whenever possible. Tensile samples were 3.25 in. long, 0.5 in. wide, and 0.040 in. thick, with a reduced section 1.25 in. long by 0.250 in. wide. The gage length used was 1 in. Electrical strain gages mounted on the

Jan 1, 1954

By K. C. Mills, E. T. Turkdogan

The results on the rates of vaporization of Fe-Ni alloys, levitated by an electromagnetic field in a stagnant atmosphere of helium, are shown to be in close agreement with those predicted theoretically. AS shown in Part I of this series of papers, the rates of vaporization of metals enhanced by convection currents are increased further by the process of condensation of metal vapor when there is a steep temperature gradient in the boundary layer. At the time this theoretical work was completed one of the authors (K. C. Mills) had already carried out some experimental work on the rates of vaporization of molten Fe-Ni alloys. The experimental work was done under conditions which make it possible to compare the experimental rate data with those predicted on theoretical grounds. EXPERIMENTAL The object of the experiments was to evaluate the activities in a number of binary metal systems. The details of the experimental technique are given in another paper by Mills, Kinoshita, and Grieveson,2 and, for the present purpose, a brief mention of the relevant features of the experimental method will be adequate. Using an induction coil, the metal weighing about 1 to 1.5 g was levitated by the electromagnetic field in a stagnant atmosphere of pure helium. The helium was freed from oxygen and water vapor in the usual manner, and its pressure in the vaporization chamber was maintained at 1 atm through a bleeder device. The vaporization chamber consisted of a pyrex tube, 2.8 cm diam, with a side arm connected to the helium bleeder. The bottom of the tube, shaped conical, was surrounded by the induction coil, and the top was sealed with an optical flat for the purpose of measuring the melt temperature with a two-color optical pyrometer. By suitable adjustment of the high-frequency power input, the metal was brought to the desired temperature in about 30 sec of levitation. After a specified vaporization time, e.g., 3 to 4 min, the alloy was quenched by switching off the power. The amount of metal vaporized was determined from the difference between the initial and final weights of the sample. During the vaporization time, temperature fluctuations of about ±10°C were observed. COMPARISON OF EXPERIMENTAL DATA WITH THEORETICAL VALUES The experimental results are given in Table I. As already mentioned, the attainment of the vaporization temperature took about 30 sec from the moment of levitation. Therefore, the times recorded in Table I are 30 sec less than the total time; this is considered to be a reasonable estimate of actual vaporization times.

Jan 1, 1964

By V. Niemitz

Approximately 30 miles east of Chicago on the southern shores of Lake Michigan stands Bethlehem Steels newest fully integrated steelmaking facility-the billion dollar Burns Harbor plant. The first phase of what will ultimately be the most completely integrated and flexible materials handling system for a steel mill in the western hemisphere is now complete.

Jan 1, 1970

By L. Casagrande, C. O. Brawner, D. L. Pentz, B. Kennedy, E. Hoek, H. Q. Golder, K. Barron

H. L. HAMMERSLEY, B. C. Dept. of Mines. I would like to ask Mr. Brawner if the direction that he measured in the boreholes with the camera was referenced to magnetic north? MR. BRAWNER. Yes, it was. However, there is one problem that you may encounter if the ore body is magnetic; the borehole compass will give erroneous results. Three procedures are available to overcome this. The first one involves the use of a gyro compass instead of a magnetic compass. The second technique developed by Christiansen in Salt Lake City, is to orient the core with the use of scribing knives. The third method is to remove the compass needle and place a steel ball in the compass case. The hole must be drilled at a slight angle off the vertical. The location of the steel ball, which will roll to the underside of the hole is photographed. A borehole directional survey is then made, from which the bearing of the steel ball relative to the axis of the compass can be determined. The joint orientation is then related to this bearing at all depths. J. ROBINSON, B. C. Dept. of Mines. It was stated this morning that there have been some recent developments that give us the ability to drill horizontal drainage holes and install drainage pipes more cheaply than in the past. Would Mr. Brawner tell us some of the new developments and methods of installing these horizontal drain holes? MR. BRAWNER There are two zones in which you may be concerned about installing drains; the first is in the overburden soil, the second is in the rock. Each area requires a different installation method. If the rock is fairly massive and the holes will remain open, the simplest procedure is to use standard air track equipment or a percussion drill. At one of the mines in the Highland Valley, drains up to 300 ft. long have been installed with a percussion drill at a rate of one drain per day. The costs were in the order of $2.30 and $2.40 per foot. If the rock is quite soft, such as in a serpentine, it will be necessary to install a casing in the hole. The least expensive casing that will not deteriorate within the life required should be used. Plastic pipe or black iron pipe are commonly used. In soft rock, it may be necessary to drill with a casing to prevent the col-

Jan 1, 1971

By Harold M. Feder, Irving Johnson

Tkermodynamic functions for dilute solutions of uranium in liquid cadmium were obtained from galvanic cell measurements. Deviations from Henvy's law were observed at concentvations down to 2 x 10-3 atom fraction. Unusually large negative values of the pavtial molal relative enthalpy and excess entvopy of uranium, suggestive of the occu,vvenctwe of partial ovdering of cadmium around uranium in these solutions, were found. The negative relative partial molal enthalpy of uranium at the liquidus accounts for the observed retrogvade solubility of metallic uranium between 473" and about 630°C. The standard free enevgy of formation of UCd,, from a-uranium and liquid cadmium is given by F,° THE constitutional diagram of the U-Cd system,' Fig. 1, is unusual in several respects. The near equality of the Goldschmidt atomic radii2 (Cd, 1.52A U, 1.56A) might be expected to give rise to extensive mutual solubility of the elements except for the restrictions imposed by differences in valence and electronegativity.3 The latter factors must be strongly influential because mutual solubilities in the terminal solid phases are probably negligible, and the solubility of uranium in liquid cadmium in the readily accessible range is only about 1 at. pct. Interestingly, the solubility of uranium in liquid cadmium actually decveases slightly with increasing temperature from 473" to about 630°C. Such a retrograde solubility in a liquid phase is a rare phenomenon in metallic systems; no other authenticated examples were found among the nearly 700 binary phase diagrams compiled by Hansen and Anderko.2 These observations suggested the existence of some unusual interaction between uranium and cadmium. Greater insight into the nature of this interaction was sought by measurement of the thermodynamic properties of the system. EXPERIMENTAL PROCEDURE The emf of cells denoted by the scheme was measured. Each cell consisted of two uranium and two alloy electrodes immersed in a molten lithium chloride-potassium chloride eutectic mixture containing uranium trichloride. The physical arrangement is shown in Fig. 2. The potential between any pair of electrodes could be measured with a Leeds and Northrup Type K-3 potentiometer. The measurements were made at points marked in Fig. 1. It should be noted that points on the phase boundaries represent the concentrations of uranium in the saturated liquid phases of heterogeneous alloys. Uranium Electrodes. Uranium, which is not a particularly soft metal, is capable of retaining residual stresses, and its potential may depend upon its physical condition. Electrodes were prepared from 3-mm diam rods of hot-rolled high-purity4

Jan 1, 1962

By B. N. Das, H. E. LaBelle, G. A. Wolf

ZnxHg1-xTe and GUPxAS1-x crystals have been grown from solution by a traveling heater method (THM). In a floating zone type fashion a solution zone sandwich of liquidus composition is made to migrate through feed material of solidus composition by a slow-speed movement of <0.25 mm per hr of the total charge through a stationary radiation or rf heater. ZnxHg1-xTe of composition 0 < x < 0.3 and GUPxAS1-x of composition 0.5 < x < 0.7 have thus been grown from their solution in liquid tellurium and gallium, respectively. A simplified analysis of heat and material transport is given. In this method, Proper adjustment of the temperature distribution along the liquid solution zone axis eliminates instability of the crystal growth front and constitutional supercooling. 1) ZnxHg1—xTe: The solid-solution telluride was grown in sealed quartz tubes at a temperature of 500 to 650°C. For first Preparations mechanical mixtures SINGLE crystals of solid solutions of III-V and II-VI compounds have been grown by various techniques from the melt, from the gaseous phase, or from solutions in of ZnTe and HgTe were used. X-ray determinations showed the resulting crystals to be homogeneous throughout their entire length, except for the end sections. The homogeneity is greatly improved by reusing the ingots obtained from first Preparations as feed material in subsequent crystal growth runs. Ingots of up to 4.5 cm have thus been obtained. 2) GaPxAs1-x: Crystals were grown in a EN crucible at a temperature of 1050°C. For first Preparation a mechanical mixture of Gap and GaAs was cemented together by a minimum amount of liquid gallium through "wet" grinding of Gap and GaAs crystals in the liquid metal and subsequent exuding of excess gallium by compacting of the charge in the EN crucible. Electron microprobe measurements using P-Ka and As-Ka radiation showed uniformity over a length of 0.4 cm. Properties of the various Preparations are described. liquid metals.&apos;-&apos; Their growth from the melt by passing a liquid zone of pseudobinary liquidus composition through a solid rod of solidus composition is generally a convenient method of growth of single crystals of solid solutions of homogeneous composition. This method loses much of its usefulness, however, if the melting point or the vapor pressure of the solid solution is high. In the case of a compound having a high melting

Jan 1, 1969

HenRy Clay FRick, a pioneer in modern coke and steel industry and, in more recent years, one of the outstanding financiers of America, died on Dec. 2, 1919, at his home on Fifth Avenue, New York. Although he had been ill since election day, when he had an attack of indigestion which developed into ptomaine poisoning, his death was a surprise to all. He is survived by his widow, Adelaide Howard Childs Frick; a son, Childs Frick, one unmarried daughter, Helen C. Frick, and four grandchildren. A quiet funeral service was conducted at the Frick home on Wednesday afternoon by the Rev. Dr. Leighton Parks, pastor of St. Bartholomew&apos;s Episcopal Church. This was attended by members and very intimate friends of the family, Trustees of the Metropolitan Museum of Art, Officers of the Links Club, and Directors of the United States Steel Corpn. Henry Clay Frick was born Dec. 19, 1849, in West Overland, Westmoreland Co., Pa. His father, John W. Frick, was a farmer of Swiss ancestG, and his mother, Elizabeth Overholt Frick, a member of an old Mennonite family. Until he was sixteen, he spent his time at school, on his father&apos;s farm, and in his grandfather&apos;s distillery, where he kept books. He attended Otterbein University, in Ohio, for a year. Frick, learning that coke was an essential of the already rapidly developing steel business, early invested every cent he could get in coking-coal lands. With the help of an associate of his grandfather, he formed the corporation of Frick & Co., coke dealers, and acquired fifty-one ovens in the Connellsville region and 300 acres of soft-coal lands. During the panic of &apos;73, with the help of Judge Thomas Mellon, a Pittsburgh &apos;banker, he bought out his partners and while coke was selling at 90 cents a ton enlarged his purchases of suitable lands. Later, the price of coke increased until it was selling at $5 a ton. Before he was 30 years old, Frick was rated a millionaire. Association with CaRnegie In 1878, he sold an interest in the business Do E. M. Ferguson of New York, and later a share to Mr. Ferguson&apos;s brother. Four years later the business was reorganized into the H. C. Frick Coke Co. with vast coal lands, great banks of ovens, and a capitalization of $2,000,000. Then began his association with Andrew Carnegie. He exchanged a part of his coke interest for shares in Carnegie Brothers of Pittsburgh,

Jan 1, 1920