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By G. K. Dumbauld, B. E. Morgan

A satisfactory well-cementing composition must retain its fluidity long enough to be pumped into Place; then it must develop within a reasonable length of time sufficient strength and impermeability to anchor the casing in position and to form an effective seal between the casing and the formations. These properties may be evaluated by pumpability, strength (compressive or tensile), and permeability tests. Laboratory test procedures for the determination of pumpability time and strength development have been outlined previously and are readily available,1 but a satisfactory and convenient laboratory procedure for the measurement of the permeability of set cement has not been developed heretofore. some permeability data have been obtained previously by passing air through dried cement specimens.2 such a procedure is unsatisfactory because the drying of set cement alters it physical and chemical properties and subjects it to conditions dissimilar to well conditions. A more realistic method would be one wherein the cement remains water-saturated durin

Jan 1, 1952

By J. L. Giove, J. M. Hodge, R. G. Storm

The hardenability effect of molybdenum has been evaluated by a number of investigators, including one of the present authors.1,2,3,4,6 Considerable discreMncy exists, however, among the results of these various investigators, and two of them, Brophy3 and Kramer,4 have indicated that the apparent hardenability effect of molybdenun would vary, depending upon the other alloying elements in the steels being considered. The results of previous, unpublished work conducted at the Duquesne Works Laboratory of the Carnegie-Illinois Steel Corporation also have indicated significant differences in the hardenability effect of molybdenu~n in nickel and in chromium steels. The present investigation was undertaken in an effort to establish the mechanism governing this difference in the hardenability effect of molybdenum. This work involved both end-quench hardenability and isothermal transformation tests on two series of steels of varying molybdenum content. One steel contained 3 pct nickel and the other 1 pct chromium. It was hoped that such studies would shed further light on the mechanism of this behavior. Materials and Experimental Work MATERIALS The chemical compositions of the steels used in this investigation arc shown in Table 1. These steels were furnished by Battelle Memorial Institutc in the form of 100-lb induction furnace ingots. The top half of each ingot was forged to 1 3/8-in. square billets and then rolled to I-in. round bar stock for isothermal transforma- tion studies. The bottom half of each ingot was forged into approximately 1 1/4-in. rounds for end quench tests. All of the steels were normalized from 1650°F and tempered at 1100°F before nlachming to end quench or isothermal samples. END-QUENCH TESTS standard l-in. diam end-quench tests were made on each of the steels. The test bars were austenitized at 1600°F for 30 min,, quenched in a standard Jominy jig, and hardness surveys were made in all tests. The 95 pct martensite point was deterInined from hardness values5 and cheeked by metallographic examination. The jominy distance values for 95 pct martensite were converted to hardellability values in terms of ideal diameter (Dl), using a revised carve for the relationship between Jominy distance and ideal diameter. This curve was based on the cooling time from the A1 to the bainite nose temperatures rather than on the usual criterion of half-temperature time. The cooling rates as determined by Russell and Williamson9 were used as a basis for this relationship. The derivation of this curve is described in detail in the appendix. ISOTHERMAL TRANSFORMATION STUDIES Samples for the isothermal transformation studies were quarter sectors of 1/16.is-in. thick slices from the 1-in. round bars. All samples were austenitized for a total the of 15 min., transferred rapidly to a lead bath for isothermal transformation, and brine quenched from the lead bath. A time of 3 see was allowed for the sample to come to the temperature of the lead bath, and this time was not included in the isothermal transformation times. Each sample was examined metallo-graphically at a magnification of 100 diam. The per cent transformation was estimated by comparison with standard micrographs, and the values were plotted against the on log/log coordinate paper. At least 4 and as Inany as 10. points were plotted for each steel. A line was drawn through the points for each steel, and the times for 5 pct transformation were obtained from the plot for each steel. Isothermal transformation diagrams in terms of 5 pet total transformation, covering the temperature range of 800 to 1200°F, were determined in this manner for an austenitizing temperature of 1600°F. The times for 5 pct transformation at the bainite nose for austenitizing temperatures of 1800 and 2000°F were also determined in the same manner. These times for 5 pct total transfor-

Jan 1, 1950

By P. Pietrokowsky, T. E. Tietz, J. E. Dorn

The amount of solid solution hardening in aluminum alloys was found to be dictated by two factors: the lattice strain, and the change in the mean number of free electrons per atom of the solid solution. To obtain this correlation it was necessary to assume that aluminum contributes two electrons per atom to the metallic bond. WHEN the modern scientific method of analysis was first being formulated, Francis Bacon recorded in his "Essays" (circa 1600) that "an alloy . . . will make the purer but softer metal capable of longer life." During the intervening centuries voluminous data have been reported which demonstrate that the additions of alloying elements do in fact increase the hardness and strength of the pure metals. Nevertheless, the significant details of this problem on the unique effect of each element toward enhancing the mechanical properties of alloys only recently have been subjected to systematic scientific scrutiny. The major objective of this investigation is to determine how minor additions of alloying elements affect the plastic properties of polycrystalline aluminum alloys. By means of such studies it is hoped to provide not only data on the solution strengthening of aluminum alloys, but also a body of facts which will supplement the knowledge already available on the factors responsible for solution hardening in general. A review1"10 and analysis1' of the existing data on the effect of solute elements on the plastic properties of solid solutions reveal that our current knowledge on solid solution hardening is somewhat meager, inconsistent, and inconclusive. Many of the inconsistencies are undoubtedly attributable to the influence of unsuspected factors, such as purity; or uncontrolled factors, such as grain size, on the plastic properties of alloys. Nevertheless the following conclusions might be tentatively accepted: 1. Addition of solute elements invariably increases the yield strength, tensile strength, and hardness of the host element. 2. The rate of strain hardening, in general, increases with the concentration of the alloying element. 3. The strengthening effect in ternary alloys is the sum of the individual strengthening effects of the two solute elements as measured in their binary alloys. 4. The lattice strain is one factor that affects the strengthening of the alloy but it is not the only factor. 5. A second factor might be the difference in valence between the solute and solvent metals. All of the available evidence is in complete agreement with the first conclusion; the remaining conclusions, however, are not in agreement with all of the published data, but, in each case, the major weight of the existing evidence favors these deductions. Additional investigations will be required before most of these tentative conclusions can be accepted without reservation. In the following report an extensive investigation of the plastic properties of binary aluminum alloys is described. This work was undertaken in an attempt to shed more light on the general problem of solid solution hardening. Materials for Test: Aluminum was selected as the solvent metal for the present investigation on the effect of solute elements on the plastic properties of alloys. This choice was made for several reasons: (1) There appears to be little fundamental data in the published literature on the effect of solute elements on the properties of high-purity aluminum alloys. In view of the ever increasing economic importance of aluminum, such data would be of basic interest to the metallurgists concerned with the development of new aluminum alloys. (2) Aluminum is thought to be only partially ionized in the metallic state1' and consequently it might provide more complex relationships of the mechanical properties with the concentrations of the solute elements than more simple fully ionized solvents would reveal. (3) The data on aluminum alloys will provide a broader basis for correlations between the mechanical properties of metals in general and the concentration and atomic properties of the solute elements than is now available. Some complications, however, attend the selection of aluminum: The solubility of the various elements in the alpha aluminum phase are quite restricted, and not always well known. Consequently, only dilute solid solutions are available for study. This, however, may be somewhat advantageous because the dilute solution laws presumably are simpler than those applying to concentrated solutions. In addition, strain-hardened pure aluminum is known to recover at atmospheric temperatures. Very likely its alloys exhibit slower recovery rates. Thus, the secondary factor of effect of alloying elements on recovery might complicate the data. Such compli-

Jan 1, 1951

By R. G. Green, R. L. Dowdell

LEAD POISONING as a result of eating lead pellets deposited in marsh areas is a cause of high mortality among ducks, geese, and other waterfowl ingested lead shot become trapped in the gizzard with gravel and are slowly ground away by the grit. Absorption of lead as it passes through the intestine in a finely divided state produces severe lead poisoning which is usually fatal. Ducks and geese with lead poisoning develop first a typical green diarrhea. Later, paralysis of the wing muscles prevents flight. As the poisoning continues with further grinding of the shot trapped in the gizzard, increasing paralysis reduces the bird to helpless-

Jan 1, 1937

By George C. Bravner

WITH the great expansion currently being made in the aluminum output of the United States, not only by the company that has heretofore been the sole producer but by a now organization in the field it is only natural to wonder to what degree the; ore reserves of the United States can contribute to the growing consumption. For the three-year period 1937-'39 the U.S. Bureau of Mine's figures indicate that the annual domestic production of bauxite averaged about 370,000 long tons, compared with average, annual import of about 194,000 long tons. About 85 per cent of the imports came from Surinam, nearly all of which went into aluminum manufacture. Not all of the or -kipped from mines in the United States is used to make alumimun however as Bureau figures indicate that in these three years an average of only 48 per cent of the domestic ore shipment were so used the abrasive chemical and other industries taking respectively 27, 21, and 4 per cent of the output. The recent increase in the demand for bauxite has been of course in it use for aluminum manufacture. This as is well known is largely attributable to the world race for supremacy in

Jan 1, 1941

By H. W. McCue, Henry Rogatz

Oil.—In the Texas Panhandle, during the year of 1941, 647 oil wells were drilled with a total daily initial production of 133,435 bb1.—that is, 145 more oil wells than in the previous year, with a decrease in total daily production of 5752 bbl. On Dec. 31, 1941, a daily allowable of 116,766 bbl., which was an increase of 27 per cent over 1940, was assigned to the field to be produced from 5182 wells. The total amount of oil produced for the year was 27,904,846 bbl., making a cumulative total of 404,657,324 bbl. during the past 20 years. Gas.—During the year, 52 gas wells were drilled, having a combined open flow of 2.62 billion cu. ft. per day—that is, 40 less than the number of wells drilled in 1940, with an increase in the open flow of 217,100,000 cu. ft. per day. The gas

Jan 1, 1942

By Henry Rogatz, H. W. McCue

Oil.—In the Texas Panhandle, during the year of 1941, 647 oil wells were drilled with a total daily initial production of 133,435 bb1.—that is, 145 more oil wells than in the previous year, with a decrease in total daily production of 5752 bbl. On Dec. 31, 1941, a daily allowable of 116,766 bbl., which was an increase of 27 per cent over 1940, was assigned to the field to be produced from 5182 wells. The total amount of oil produced for the year was 27,904,846 bbl., making a cumulative total of 404,657,324 bbl. during the past 20 years. Gas.—During the year, 52 gas wells were drilled, having a combined open flow of 2.62 billion cu. ft. per day—that is, 40 less than the number of wells drilled in 1940, with an increase in the open flow of 217,100,000 cu. ft. per day. The gas

Jan 1, 1942

By R. I. Garrod, R. A. Coyle

The shapes and positions of X-ray reflections from specimens of copper, steel, and aluminum alloy haue been examined in the elastic and plastic ranges both while the specimen was under stress and in the unloaded condition. For the aluminum alloy the shape was unaltered by the application of stress either within the elastic limit or in the plastic range provided that no additional plastic strain was induced. In copper the broadening accompanying plastic deformation was very slightly reduced when the specimen was unloaded. A similay but more marked elastic component of broadening was also found for steel, but in this case below the yield stress. Line profiles corrected for instrumental and particle-size broadening indicate very large internal stresses in local regions of the plastically deformed metals. The results are discussed in terms of a recent suggestion that the heterogeneous dislocation distribution between the cells and their boundary walls plays a major role in the peak shifts and broadening of the X-ray reflections. STUDIES of the X-ray line profiles from strained polycrystalline aggregates concentrate usually on one or the other of two main parameters: a) the displacement of the peak of the intensity contour from its position for a strain-free aggregate, or b) the shape of the profile. From peak shifts data can be obtained either on the relation in both the elastic and plastic ranges between applied external stress and average lattice strains in a given (hkl) direction, or, alternatively, on the residual lattice strains which are present after a plastically deformed specimen is unloaded.' On the other hand, the shapes of the broadened profiles from cold-worked metals can be analyzed to separate the broadening produced by small particle size and by heterogeneous lattice strains.' In this paper the terms "size broadening" and "strain broadening'' are used in the general sense adopted by warren.' In the past, apart from two early qualitative observation, it has been customary to examine only the movements of the peaks of the profiles while the specimen is actually under load, since the line broadening induced by plastic strain remains after removal of the external stress. Consideration of the implications of existing data of this type suggests, however, that fruitful additional information on a number of fundamental aspects might be gained by careful examination of whether the X-ray line profile is in fact different in the loaded and unloaded states of the specimen. By taking advantage of the sensitivity and convenience of modern diffractometer techniques it is possible to explore with relative ease the magnitude and importance of any elastic effects which may be superimposed upon the well-known permanent changes in profile. The main aim of the work to be described was thus to investigate this point for typical metals and alloys. For this purpose annealed specimens were extended first elastically and then plastically and the positions and shapes of X-ray reflections were recorded. Initially it was anticipated that prime interest would center on observations within the plastic range; it has been found, however, that small changes in profile sometimes occur both before and after the nominal elastic limit of the material is reached. It is shown that the results obtained have important implications in relation to the structural changes and processes associated with deformation. I) EXPERIMENTAL To enable the diffraction lines to be recorded while the specimen was under uniaxial-tensile stress, a small hydraulic testing machine was designed and constructed for direct attachment to the goniometer of a Philips diffractometer. The specimens, which were machined from 1/2-in.-diam rod and had a central rectangular section 3/8 by 1/16 in. over a gage length of 1 in., were held in the machine by split collets mounted in grooves in the cylindrical ends of each specimen. No special precautions were taken to ensure precise axiality of loading. Constant oil pressure was maintained by a lever and weights system and transmitted to the loading rig by flexible pipe. The actual load on the specimen was measured by a load cell in the machine to an accuracy of * 1 pct. To enable smooth X-ray profiles to be obtained the specimen and machine were oscillated continuously during recording through *7-1/2 deg about the normal half-angle position of the goniometer. The three materials chosen for the investigations were high-purity copper as representative of a ductile fcc metal, a low-carbon steel for a bcc metal, and an aluminum alloy as a material in which the proof stress/ultimate strength ratio is high. Details are as follows. a) Copper. 99.999 pct purity. After machining the specimen surface was polished mechanically and

Jan 1, 1964

Jan 1, 1889

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By Jan H. Hommen

TRENDS IN MINE FINANCE Reviewing historical trends may help in dealing with future funding strategies. The first trend is the increase in the use of debt to fund corporate America. Surprisingly, when comparing that with other corporates in the global marketplace, the U.S. does not look too poorly. Japanese, in particular, but also German companies, are much more leveraged than their U.S. counterparts. Note that in Japan and Germany the government and the consumer have shown substantial restraints when it comes to credit. Not so in the U.S. where the savings rate (4%) is much lower than that in Japan (20%) and in Germany (14%). As a result, the cost of leverage is substantially lower in Japan and in Germany than in the U.S. Lower debt costs in these countries allows one to obtain more of it for the same price. The close relationships between financial institutions, corporations and governments in Japan and Germany also make the risk of leverage more bearable and understandable. Also note that interest rate volatility in these countries is more subdued. The investor base in common stock is also changing. Private pension funds have been net sellers of equities during the last few years while public pension funds have been net buyers. Individuals are basically out of the market. It is estimated that over $330 billion of equity was retired in the U.S. through 1986-1988. The reasons are well known: restructurings, buy-backs, takeovers, mergers, and buy-outs. This de-equitization is likely to continue as the cost of equity capital is higher than the cost of debt capital, even on a before-tax basis. Because there has been no market for equity since October 19, 1987, junk bonds have replaced equity capital in the corporate finance structure. The non-investor-grade borrower has access to the public markets through high-yielding debt securities that often look like senior equity. Deregulation has also provided 24-hour markets; securitization can now liquify assets that before were rusting on balance sheets; information processing and communication tools give facts that are instantaneously available, creating the need for products to cover risk and exposures unknown before the start of the information and technology explosion. Thus we now have swaps, options, futures, options on futures, caps, as well as program trading, portfolio insurance, index funds, etc. Globalization will be unstoppable. Today&apos;s environment demands it. Corporations are now global competitors, even though they may have never shipped a product off-shore. Boundaries are disappearing and impediments have been removed. Stocks can be issued in a global offering with distribution in all major financial centers of the world. The high leverage of Japanese companies has made common stocks very scarce, which with the high savings rate, makes equity capital inexpensive in Japan. If markets were perfect everyone would issue stock in Tokyo and buy it back in New York. This would certainly stop the bleeding on the balance of payments. With the deficit balance of payments in America, it is no surprise that the cost of money is expensive here. The risk-return relationship on U.S. equity is not favorable enough to appeal to Japanese equity investors. The Tokyo-market, helped by a stronger yen, surpassed New York as the most important equity market in the world. The question is, will the Tokyo market hold up when Japanese domestic consumption increases at the expense of savings? In the U.S. debt markets, the plain vanilla debenture is making a comeback after a period of absence. Commercial paper has replaced short term bank borrowings for working capital funding by larger corporations. The banks have made an interesting comeback with loan sale programs that will continue to attract borrowers. There will be a continuing

Jan 1, 1990

By S. A. LoPilato, J. T. Smith

SEVERAL techniques have been evaluated for cooling the throat area of rocket-nozzle inserts to prevent erosion or fracture of the inserts during exposure to high operating temperatures and pressures. Self-cooled composites, such as infiltrated tungsten, have shown considerable promise for these applications. These composites can be fabricated by infiltrating the refractory matrix with a lower-melting metal or non-metal which is insoluable in tungsten. During firing, the lower-melting substance undergoes a series of continuous endothermic phase changes which absorb sufficient heat to maintain the nozzle matrix material at or below a safe operating temperature. At present, the state-of-the-art has reached a point where the refractory matrix density and microstruc-ture have been established as the critical parameters to be controlled for optimum self-cooled performance.&apos;" Nondestructive testing has been utilized to ensure that porous tungsten billets were of uniform density and free from cracks or other defects prior to fabrication into rocket nozzle inserts. Ultrasonic-velocity techniques have been employed because of their reliability and reproducibility. The purpose of this note is to present and interpret the test data developed for porous tungsten matrices. For evaluation purposes, tungsten powders with Fisher subsieve sizes of approximately 4 and 18 p have been obtained for study from four commercial sources: the General Electric Co., Wah Chang Corp., Fansteel Metallurgical Corp., and Kennametal, Inc. Porous tungsten matrices were fabricated from the powders by hot pressing in induction-heated graphite die assemblies. Typical billets ranged from 3 in. diam, 2 in, high to 5 in. diam, 5 in. high. The ultrasonic-velocity measurement technique employed was through transmission, pulse echo at a frequency of 1.0 mc using matched barium titanate crystal transducers. The testing equipment included a pulsed ultrasonic generator, an amplifier, a specimen holder, and an oscilloscope, as shown in Fig. 1. The porous tungsten thickness was measured to i 0.0005 in, with precision micrometers while the oscilloscope achieved 0.02 psec time measurement accuracy. The time for a sound wave to pass through the billet, the bulk wave velocity, was calculated to 0.5 pct using Eq. [l]: V-} where V = bulk wave velocity, in. per psec, T = specimen thickness, in., and / = time, psec. To develop inspection standards, the bulk density of a porous tungsten billet was determined by the ASTM water-immersion technique.3 The ultrasonic-velocity measurements were completed at seventeen positions for each billet and averaged to develop a characteristic standard velocity for a particular tungsten powder at several density levels. A plot of ultrasonic velocity vs density is presented in Fig. 2 for six different tungsten powders. This graph has been established as

Jan 1, 1967

By Herbert W. Graham

IRON ORE is widely distributed throughout the world. Ores sufficiently high in iron content to be practical for the operations of iron and steel making occur in so many places that it is only by the accident of political subdivisions that any given nation does not have adequate and suitable iron ore. Data prepared by various authorities show that in the Lake Superior region alone there are reserves of 1,200,000,000 tons of iron ore of an iron content and at the level of production cost to which the industry has been accus tomed. At an annual consumption of 80,000,000 tons these reserves will last fifteen years. Taken alone these figures would be alarming, but over a considerable period of years the total reserve tonnage has been more or less steadily increased by improvement and extension of mining and beneficiation methods. The rate of depletion of reserves has been only about one third of the rate of consumption. On this basis the cheap high-grade ores of Lake Superior would last 45 years.

Jan 1, 1947

By B. C. H. Steele, C. B. Alcock

In choosing solid oxide electrolytes for use in the measurement of thermodynamic quantities at high temperatures, the two most important criteria are the values of the partial ionic and electronic conduc tizities. Measurements of these conducticities have been made for some Group IVA oxides and solid solutions of these oxides with CaO, Y2O3, and La2O3. The total conductivities as a function of temperature. oxygen partial pressure, and composition were determined, as well as the electromotive forces of cells in which the oxygen partial Pressures of the electrodes were between 10-7 and 10-29 atm at 1000°C. Additional factors that influence the experimental arrangements, such as the operating temperature, the appropviate cell atmosphere, and electrode kinetics, are also discussed. IT has long been recognized that galvanic cells incorporating solid electrolytes can possess many advantages for the measurement of high-temperature thermodynamic data. Unfortunately, the electrical-transport properties have only been established for a few solid electrolytes, although attempts have been made, and are still being made, to use such materials as porcelain&apos; and magnesia.&apos; Kuikkola and Wagner have discussed3 and demonstrated4 various applications of solid electrolytes, and, in particular, their work stimulated the electrochemical measurement of oxygen activities using cells incorporating the solid oxide electrolyte, Zr0.85Ca0.15O1.85 The excellent characteristics of this oxide electrolyte have been confirmed by the investigations of Kingery et al.5 (oxygen ion diffusion), Carter and Rhodes6 (zirconium and calcium ion diffusion), and Weissbart and Ruka7 (electronic transference number). However the observations of Peters and Mobius,8 later confirmed by Schmalzried,9 indicated that the electronic component of zirconia-based electrolytes could become significant at low oxygen chemical potentials. Under these conditions, thoria-based electrolytes have obvious advantages arising from their superior thermodynamic stability. It was known that certain thoria solid solutions possessed defect fluorite structures containing anionic vacancies (cf. Zro.85Cao.l50O1. 85), although data on their electrical properties were conflicting. Kiukkola and wagner4 concluded that thoria-based electrolytes exhibited appreciable electronic conductivity, whereas Peters and Mobius8 mentioned that the electronic conductivity only became important at high oxygen partial pressures, but gave no further details. In addition, both Kiukkola and wagner4 and Peters and Mann&apos;" had determined the oxygen chemical potentials associated with the Fe-FeO, Co-COO, Ni-NiO, and Cu-Cu2O equilibria, and it was not known whether discrepancies in their results could be attributed to the different cell design, or the thoria-based electrolyte used by Peters and Mann. These uncertainties have been resolved during the present investigation into the measurement of low oxygen chemical potentials, and transport properties of the relevant oxide electrolytes are presented and discussed. Other experimental difficulties associated with low oxygen chemical potential measurements are also described, with particular reference to the Nb-O system. 1. THEORETICAL CONSIDERATIONS Oxide systems of potential use as solid electrolytes possess a large energy gap between the valence and conduction bands. Little is known about the defects present in these wide-gap metal oxides as a function of impurity content and deviations from stoichiom-etry, or the mechanisms by which electronic charges move in these solids. For these materials it is convenient to represent the measured conductivity as the the sum of three terms: where a, is the conductivity due to positive hole conduction (p type), and oe is the electronic conductivity due to electron conduction (n type). U there is a large concentration of ionic vacancies fixed by composition then the ionic contribution will not be a function of oxygen pressure. Although the possibility of a pressure-independent electronic component also cannot be ignored, it is likely that such a term would only become significant at very high temperatures, and in general the positive hole conduction will increase with increasing oxygen pressure, and the electron conduction will increase with decreasing oxygen pressure. It follows that the total conductivity is related to oxygen partial pressure as follows:

Jan 1, 1965

By Enrique Hauser

FiRE-damp is a mixture of methane with other inert gases or combustible gases. The inert gases in question are carbonic acid, water vapor, nitrogen, etc. The combustible gases are hydrogen, ethane, etc. The study of the properties of fire-damp, therefore, becomes a study of the properties of methane and the influence on its properties of the different gases we have mentioned. Characteristic Properties of Methane 1. Respirability.—Methane being a paraffin is characterized by its weak chemical affinities. Prom the physiological point of view one could substitute it for nitrogen of the air at least momentarily, without experiencing any difficulty in breathing the mixture consisting of 21 per cent. 02 + 79 per cent. CHI. I have tried this on myself, making the gas exhaled from the lungs burn subsequently in a Bunsen burner.&apos; From the chemical point of view, this weak affinity permits the gas to be burned in certain circumstances with hydrogen and oxide of carbon in an oxygenated mixture, with the result that the last two gases achieve only a fractional combustion. This practice has been utilized with success in the methods of analysis which I have perfected and which I describe later in this paper. 2. Retardation of Flashing Point.—A characteristic property of methane is its retardation of flashing point, noted by Davy in 1816 and studied by Mallard and Le Chatelier in 1883.2 Taffanel and Le Floch have recently confirmed these results.8 Let us recall the nature of this retardation: When a mixture of combustible gases with air or with oxygen is

Jan 1, 1916

By F. M. Yans, A. D. Donaldson, A. R. Kaufmann

Beryllium was mixed by powder. metallurgical techniques with copper, nickel, iron, and chromium, respectively, to form beryllium -rich binary alloys which Mere then extyuded and rolled transtverse to the extrusion direction. The effect of each alloying element was determined by tensile testing. In solid solution, small amounts of iron and nickel had an embrittling effect, while copper in solution increased the strength but had no effect on ductility. The effect of chromium was complicated and not readily explainable. Observations concerning the planes and modes of fracture were made. BERYLLIUM possesses some very attractive properties for general design applications, especially its strength to weight ratio which is approximately twice that of aluminum and three times that of stainless steel. Equally significant, however, is its combination of high moduli , high strength (approximately 70,000 psi tension and 40,000 psi shear), and low density (0.0658 Ib per in.3), which has made it a potentially important structural material for use in high-speed aircraft and missiles. The main attractions of beryllium are most marked when compared to other constructional alloys now in use. For example, while its density is approximateiy that of magnesium, its modulus of elasticity is approximately seven times that of magnesium, three times that of titanium, four times that of aluminum, and 1 1/3 times that of steel. Furthermore, its relatively high strength and high melting temperature permit design for service temperatures to about 1100°F. It is felt by the aircraft industry in general,&apos; that the high cost of beryllium can easily be amortized by the savings in fuel costs, and increases in aircraft payload and range. The only factor which has prevented the use of the metal in structural applications is its lack of sufficient ductility. It is this property that has retarded the development and utilization of beryllium. Beryllium&apos;s modes of deformation, Fig. 1 indicate that the main fracture planes at room temperature in a randomly oriented sample are the (0001) basal planes; the (1150) prism planes are the planes of secondary fracture.&apos; Klein, Macres, Woodard, and Greenspan3 obtained elongations of up to 40 pct in beryllium sheet rolled above 700°C when the (0001) basal planes were oriented parallel to the plane of the sheet (see Fig. 2).

Jan 1, 1962

By T. L. Fritzlen

Extrusion of aluminum alloys in this country is performed mainly by direct extrusion, therefore this paper is confined only to factors affecting the rate of extrusion by this method. Many factors affect the rate of extrusion of aluminum alloys. It is the purpose of this paper to present a discussion on the factors that are subject to technical control. Most of them are closely related, so that a clear-cut distinction between them is rather difficult. However, an attempt will be made to evaluate the effect of each factor separately, as far as possible. The most important factors only will be considered, and these will be discussed in detail under three general headings: (I) characteristics of the equipment, (2) size and structure of the ingot, and (3) temperature of ingot, cylinder, and other parts. It is a well established fact1 that the pressure and the speed of extrusion are related and are exponential functions of one another. Therefore, whenever a certain condition tends, for instance, to increase the pressure required for extrusion, it will reduce the extrusion speed if the pressure is maintained constant. For this reason, in this paper the effect of various conditions is expressed either in regard to their effect on the pressure required or the extrusion speed. Another established fact is the relation- ship between the temperature of the material being extruded and the pressure required to extrude. According to Schi-shokin,= this relationship is of the exponential type, and as the temperature is increased the pressure required is decreased. It would seem from the preceding that the greatest rates of extrusion can be obtained by the use of higher temperatures. However, as is well known, other factors intervene to limit the rate of extrusion of aluminum alloys when increasing the temperature. These factors will be discussed in detail later. Characteristics of the Equipment The capacity of the press determines * the maximum unitary pressure that can be applied for any given cylinder diameter. Pressures used for extrusion of aluminum alloys range from approximately 50,000 lb. per sq. in. to 150,000 lb. per sq. in., dependent upon the alloy and the size of the shape extruded. Higher pressures could be used to advantage, but existing steels limit pressures employed in the production of extrusions. Numerous mechanical characteristics of the extrusion press affect extrusion rate. The most important characteristics of the press itself are: (I) sensitivity of the main pressure valve and accuracy of pressure gauges, (2) accuracy of equipment to heat the cylinder uniformly and to control cylinder temperature, and (3) accuracy of means of measuring the speed of extrusion. The variables subject to control during the extrusion operation are pressure, temperature, and speed, and it is evident that the preceding characteristics

Jan 1, 1946

By T. L. Fritzlen

Extrusion of aluminum alloys in this country is performed mainly by direct extrusion, therefore this paper is confined only to factors affecting the rate of extrusion by this method. Many factors affect the rate of extrusion of aluminum alloys. It is the purpose of this paper to present a discussion on the factors that are subject to technical control. Most of them are closely related, so that a clear-cut distinction between them is rather difficult. However, an attempt will be made to evaluate the effect of each factor separately, as far as possible. The most important factors only will be considered, and these will be discussed in detail under three general headings: (I) characteristics of the equipment, (2) size and structure of the ingot, and (3) temperature of ingot, cylinder, and other parts. It is a well established fact1 that the pressure and the speed of extrusion are related and are exponential functions of one another. Therefore, whenever a certain condition tends, for instance, to increase the pressure required for extrusion, it will reduce the extrusion speed if the pressure is maintained constant. For this reason, in this paper the effect of various conditions is expressed either in regard to their effect on the pressure required or the extrusion speed. Another established fact is the relation- ship between the temperature of the material being extruded and the pressure required to extrude. According to Schi-shokin,= this relationship is of the exponential type, and as the temperature is increased the pressure required is decreased. It would seem from the preceding that the greatest rates of extrusion can be obtained by the use of higher temperatures. However, as is well known, other factors intervene to limit the rate of extrusion of aluminum alloys when increasing the temperature. These factors will be discussed in detail later. Characteristics of the Equipment The capacity of the press determines * the maximum unitary pressure that can be applied for any given cylinder diameter. Pressures used for extrusion of aluminum alloys range from approximately 50,000 lb. per sq. in. to 150,000 lb. per sq. in., dependent upon the alloy and the size of the shape extruded. Higher pressures could be used to advantage, but existing steels limit pressures employed in the production of extrusions. Numerous mechanical characteristics of the extrusion press affect extrusion rate. The most important characteristics of the press itself are: (I) sensitivity of the main pressure valve and accuracy of pressure gauges, (2) accuracy of equipment to heat the cylinder uniformly and to control cylinder temperature, and (3) accuracy of means of measuring the speed of extrusion. The variables subject to control during the extrusion operation are pressure, temperature, and speed, and it is evident that the preceding characteristics

Jan 1, 1946

By L. A. Roe, John Jan

Iodine is a soft, lustrous, grayish-black nonmetallic element with a density of 4.9. It is the least active of the four members of the halogen family. The other members are, in order of increasing activity, bromine, chlorine, and fluorine. Iodine is a solid at ordinary temperatures, while bromine is a liquid and chlorine and fluorine are gases. Iodine melts at 113°C and volatilizes at 184.4°C to a blue-violet gas with an irritating odor. It occurs in nature only as iodates and iodides or other combined forms. It was discovered by Bernard Courtois in France in 1811, who noticed its presence as an unknown substance in crude soda ash obtained from burning seaweed. Gay-Lussac recognized it as a new element and named it iode, from the Greek word "ioeides or iodes" for violet color (MacMillan, 1970). The world production is not known with any great certainty, but it is probably between 25 and 35 million lb per year, of which about 30% is consumed in the United States. Geology and Mineralogy Iodine compounds occur as a minor constituent as a mineral in the Chilean nitrate deposits and in solution in brines and seawater. According to the US Geological Survey, it is the 47th most abundant element in the earth&apos;s crust. The minerals lautarite, Ca (I03)3 (calcium iodate), and dietzeite, Cat (103)2 (CrO4), (calcium iodate-chromate) are found in Chilean nitrate deposits which are located in Antofagasta and Tarapaca provinces on the eastern slope of the coast range in a desert area. Various brines contain iodine compounds. Seawater contains about 0.05 ppm of iodine and some seaweeds will extract and accumulate it up to 0.45% on a dry basis. Some coals in West Germany also contain iodine compounds. The known and potential sources of iodine reported in 1968 are given in Table 1. Table 2 lists estimated world iodine reserves. Iodine has been recovered from brines in Java, Indonesia, France, England, and the USSR. Iodine has also been recovered from seaweed in Ireland, Scotland, France, Japan, Norway, and the USSR. The indicated reserves and future resources of iodine are large but have never been adequately measured. Analysis Iodine as the free element can be detected by the characteristic blue color it gives to a starch solution. Quantitatively it is determined as the free element by titration with standard thiosulfate solutions using starch as an indicator. Colorimetric methods are also applicable. Markets and Prices Iodine and its compounds are generally marketed in the form of: iodine, crude; iodine, resublimed; calcium iodates; calcium iodide; potassium iodide, sodium iodide, and numerous organic compounds. Product Specifications Crude iodine, World market: 99-99.5% 12. Crude iodine, US produced, average: 99.8% 12. Crude iodine, USP XVII Specs: not less than 99.8% percent I2. Resublimed iodine is usually 99.9% and ACS specifications call for not over 0.005% total bromine and 0.020% nonvolatile materials (Anon., 1971). Prices, c.i.f. United States, for iodine have been steadily increasing from $1.18 per lb of crude in 1967 to $6.37-7.27 in January 1981 (Anon., 1981). In 1980 the price of iodine increased by 50%.

Jan 1, 1983

By E. M. Kalar, I. Iwasaki, J. D. Zetterstrom

Several methods of removing fatty acid coatings from iron ore flotation concentrates were tested both on a Mesabi oxidized iron ore and on a magnetic taconite concentrate, and their effects on the duplex flotation process and on pelletizing were compared. Either acid or alkali alone could not remove the coatings, but a combination of such reagents as lime and quebracho, calcium chloride and pyrophosphate, or sulfuric acid and an organic acid (oxalic, malonic, or citric acid) was quite effective. The use of activated carbon was found to be particularly promising. The removal of fatty acid coatings from iron ores is of much practical interest when a pelletizing process is being considered for a concentrate floated with a fatty acid collector or when a duplex flotation process is being considered for upgrading an oxidized iron ore. A duplex flotation process is a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process is being used in the Florida phosphate fields.&apos; Although in northern Michigan mills fatty acid flotation concentrates have been pelletized successfully, at other locations fatty acid coatings on iron flotation concentrates have proved so undesirable in the agglomeration operation that other methods of concentration had to be sought.&apos; Since fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates, a combination of reagents, such as lime and quebracho,3 lime and alkali phosphate,4 or sulfuric acid and oxalic acid,&apos; has been proposed. It was also thought that activated carbon might be effective in removing fatty acid coatings due to its high adsorptive capacity. Activated carbon, with its enormous surface per unit of volume, is well known for its exceptional efficiency in removing organic pollutants from industrial effluents. This article presents the practical aspects of the above methods when they are applied to the duplex flotation process and to the pelletizing of iron flotation concentrates. The article also includes a preliminary investigation of the common parameters involved in the depressant activity of the reagents. EXPERIMENTAL WORK Initially, the experimental work was directed towards the optimization of each method for the removal of hydrophobic coatings from iron oxide surfaces floated with fatty acids. Subsequently, the methods thus optimized were tested in the duplex flotation process with an oxidized iron ore and in the pelletizing process with a magnetic taconite concentrate. Preliminary Flotation Tests: Although the three types of chemical treatment reported in the literature were briefly investigated for the purpose of comparison, major emphasis was placed during the preliminary flotation tests on the use of activated carbon because it was thought to have certain advantages over the chemical methods. LIME AND QUEBRACHO - To obtain a flotation concentrate for optimizing the lime and quebracho method of fatty acid removal, the magnetic taconite concentrate was used. The concentrate had a size consist of 90% passing 325 mesh and analyzed 64.5% iron. After a few preliminary tests the fatty acid flotation procedure with the magnetic taconite concentrate was standardized as follows. A 1200-g sample of the magnetic concentrate was pulped in a Fagergren laboratoy flotation cell to 40% solids, conditioned with 0.5 lb of soda ash per ton for 2 min, and then further conditioned with 1.0 lb of Acintol FA-2 per ton for 2 min. After 5 min of flotation, recovery was nearly complete, averaging 98.6% of the weight and 98.7% of the iron. The cell product, which amounted to 1.4% by weight and analyzed 63.2% iron, consisted mainly of relatively coarse middling particles. Since the repro-ducibility of the flotation concentrates produced by this procedure was vey high, the same procedure was used to prepare fatty acid concentrates for each of the six tests of the lime and quebracho method. To test the removal of the fatty acid from the magnetite surfaces by the lime and quebracho method, a fatty acid froth product was returned to the flotation cell, repulped by 30 sec of agitation, and then con-

Jan 1, 1968