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By M. M. Neale

The pottery department has been aptly described as the "heart of the zinc plant," md every operator of a horizontal-retort plant is acquainted with the fact that good retort practice is the keystone of the smelting process. Since retorts and condensers are clay products, it is obvious that improvements in other branches of the ceramic industry should be observed for possible adoption in the pottery process for zinc smelting. Deaeration of clay bodies is one of the improvements that have become fully, established in many brick and pottery plants. Our investigation of a number of these installations always yielded the same answer—improved practice. Improvement in workability, elimination of laminations, less porosity, greater wet and dry strength, were among the claims put forth for this process. All of these features are exceedingly desirable characteristics in the manufacture of a zinc retort. A preliminary test, which involved truck transportation of deaired slugs over a relatively long distance, did show the value of many of these characteristics in forming the retort. Results from the standpoint of , longer retort life in the smelting furnace were not outstanding. The idea lay dormant for several years but was revived again in 1940, when it was decided to make whatever changes were necessary in the equipment for pottery manufacture to fully demonstrate the process. A number of the manu- facturers of machinery for clay work were asked to submit proposals, and the plan finally adopted was extremely simple and economical. Machine FOR DeaeRRATING Selection of the ''Straight-line'' principle for conversion of the "Wettengel" pug mill to a ''vacuum-extrusion" machine preserved some usable parts of the original equipment, such as the drive mechanism, and main shaft. The converted machine consists of a feed hopper, a compression and shredding zone, a vacuum chamber, and an extrusion barrel, as shown in Fig. I. In operation the clay mix travels from the feed hopper into the compression zone, where it is compressed and finally forced around the tapered cone into the vacuum chamber. As it enters this chamber the clay body is shredded into thin plates, for exFosure to the vacuum. The shredder consists of a hub mounted on the main shaft, to which are bolted segmental sections, each of which carries shredder knives. The compression zone and extrusion barrel function as seals for the vacuum chamber and the shredded clay mix is agitated thoroughly during its exposure to the vacuum. A vacuum pump, equipped with a 3-hp. motor, is attached to this chamber, and maintains 25 to 26 in. vacuum during operation of the mill. Changes in Practice Prior to the adoption of the deaeration process, our standard pottery practice called for double mixing in the combination 7

Jan 1, 1944

By Peter Allen, John R. Stuermer

COUNTRY RISK ANALYSIS A company operating in a foreign country assumes all the risks that it would at home. However, beyond these, it assumes risks that arise from the unique political economic, financial conditions of the foreign country which it operates. These risks are known as "country risks". The importance of these risks has grown appreciably in the recent past (particularly in the aftermath of Iran's revolution in the late 1970s and Mexico's debt rescheduling of 1982-83), and as a result, country risk analysis has become an increasingly useful management tool. Country risk analysis seeks to assess the probability that countries will service their aggregate foreign liabilities on time, as well as the probability that country conditions could inhibit the debt service capability of private sector debtors. This involves assessment of both the ability and the willingness of countries to meet their external liabilities in a timely fashion. "Ability" is linked economic and financial variables: principally, a country's economic structure, foreign exchange generating capacity and debt service burden. On the other hand, "willingness" is tied to political factors: mainly the economic/financial orientation of government policy and the stability of economic decision making. Ability: Economic, Financial Conditions and Prospects Judgement of a country's ability to meet foreign financial obligations begins with a detailed study of a country's external balance sheet which compares the country's foreign liabilities and assets. Table 1 below presents country balance sheets for Mexico, Korea and Indonesia. [TABLE 1 The External Balance 3-,-et 1983 (billions of dollars; Indonesia Mexico Korea Foreign Liabilities 31.1 67.6 40.5 By Source: Bank 13.1 75.5 26.3 Non-bank 18.0 12.114.2 Foreign Reserves 9.3 4.7 7.0] The large magnitude of Mexico's external debt (nearly $90 billion), compared to foreign assets of approximately $5 billion, illustrates the weakness of this country's external payments position, and the main reason that it has been unable to meet interest and principal payments and been forced to reschedule its foreign debt. On the other hand, the relationship between Korea's external liabilities and assets ($50.5 billion and $7 billion, respectively), is more favorable and helps explain why Korea has been able to meet debt service payments and maintain its access to the international capital markets. Indonesia has even a more favorable relationship between its foreign assets and liabilities, $31 billion and $9 billion, respectively, and its debt is mostly lower interest rate, non-bank debt, making for a less onerous debt service burden. After the balance sheet, the analysis turns to a comparison of the country's foreign exchange earning capacity and its prospective financing requirements, that is, the country's future earnings stream

Jan 1, 1985

By G. R. Speich, L. Zwell, H. A. Wriedt

HORNBOGEN1 has recently shown that it is possible to measure the degree of segregation accompanying cellular precipitation in ferritic Fe-Zn alloys by measuring the lattice parameter of the ferrite phase within the cell. In extending this work to study a wider range of composition and to evaluate the free-energy change accompanying the growth of the cells, the lattice parameter and the boundary of the a! phase in Fe-Zn alloys were redetermined to check the earlier work of Schramm.2 This appeared to be necessary since the Fe-Zn diagram has been drastically revised since the work of Schramm. Stadelmaier and Bridgers3 have recently shown that, contrary to prior belief: the y iron field is closed and the a phase boundary extends to an a + T + L peritectic at 782°C where peritectic a contains 42 at, pet Zn. The phase T in equilibrium with the a solid solution has a composition near Fe3Zn10 and a cubic 081 type structure.' The alloys were prepared by two different methods. In the first method carbonyl iron powder (400 mesh, 99.8 pet pure) and high-purity zinc powder (200 mesh, 99.99 pet pure) were mixed in a ball mill and then pressed in a die at 40,000 psi pressure to make compacts with a diameter of 5/8 in. and a thickness of l/4 in. These were sealed in evacuated quartz capsules, gradually heated to 1100°C over a period of 1 week (3 days at 600°C) 3 days at 800°C, 1 day at (1100°C), and then quenched in iced brine. For the alloys containing 23.4 and 30.1 at. pet Zn, the final homogenization anneals were performed at 1000" and 850°C) respectively, to prevent melting. In the second method, alloys were prepared by saturating high-purity iron millings (0.001 in. thick, 99.9 pet pure) in zinc vapor. For each alloy the impregnation was conducted at a fixed vapor pressure of zinc and a fixed temperature between 750' and 800°C. When saturated, the millings were quenched in water. The compositions of the alloys prepared by both methods are shown in Table I. The lattice parameters of the ferritic solid solutions were determined by comparing the 26 values of their 310, peaks (using Co Ka) or of their 211 , peaks (using Cr Ka) with those of corresponding peaks for high-purity a iron. The 20 values were measured at room temperature with an X-ray dif-fractometer (G.E.-XRD5). By using a fiducial value of 2.8664Å for the lattice parameter of pure a iron at 25oC,5 the lattice parameters of the zinc-bearing

Jan 1, 1964

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By Lester Guttman

The connection between short-range order and thermodynamic activities in binary solid solutions has been pointed out by Birchenall1 who calculated approximate values of the energy of interaction of Zn and Cu and of the degree of short-range order in alpha-brass at one composition and two temperatures. The purpose of this note is to call attention to a somewhat more accurate theory than that used by Birchenall and to extend the calculations to a wider range of temperatures and compositions as a means of testing its applicability. This is an example of the well-known general method of comparing measured thermodynamic functions of a system with those calculated from a microscopic model by means of statistical mechanics. In this case, mathematical approximations must be used which make difficult any decision about the validity of the model. Birchenall's statistical method resembles closely that calletl by Fowler and Guggenheim2 the "quasi-chemical" method which has been shown to lead in certain cases to results identical with those obtained by the method of Bethe.3 The quasi-chemical method has been extended by Takagi4 to give general formulas for the free energy of binary solid solutions based on several lattices at all compositions and temperatures. Specifically, he treats the four systems typified by: I. ß—brass; 2. a— brass; 3. AuCus; 4. AuCu. When the temperature is so high that no long-range order exists, these formulas reduce to the same form for all lattice types, namely: F - FO = (E - EO) - T(S - S°) = ½N(c — x)(2vAB — vAa - Vbb) + M1/2KTzN[x log x + 2(c - x) log (c - X) + (I - 26 + X) log (1 - 2c + x)] -kT(z - I)N[c log c+(I-c) log (I -c)] Eq 1 Here the symbols have the following meanings: F—Helmholtz free energy E—nergy 5—ntropy k—the gas constant per molecule z—coordination number, (e.g. I2 in a-brass). N—total number of atoms c—atomic fraction of A Vaa, vbb, vab—nergy per bond of the corresponding bonds log means log, throughout The superscript ° denotes the thermodynamic fuliction in the standard state, which has been chosen to be pure A or B with the same crystal structure as the solid solution. The quantity x is the ratio of the number of A-A bonds to the total number and for minimum F satisfies the equilibrium condition Vaa + Vbb — 2Vab _ (c — x)2 kT l0g x(i - 2C + x The free energy may also be written in terms of /La and B, the chemical potentials or partial free energies per alom:

Jan 1, 1949

By J. V. Gluck

In the present paper," as in earlier publications, V1'2"1 the authors present experimentally obtained relations for the free energy of solution of oxygen in various metals as a function of temperature. The relations are linear and given in slope-intercept form. The authors give values for the "probable error" of the slope and intercept, citing Birge's method17 for obtaining these quantities. Birge discussed these methods as early as the period 1929-32.25726 In Ref. 25 the probable error is defined as "the numerical value which the true error is as likely to exceed as not", i.e., 50 pct probability. Ref. 26 is even more detailed and includes a lengthy discussion of the applicability of the Gaussian distribution to experimental data. However, the use of the "probable error" has come under some question. For example, Ezekiel'~ states that "the use of the probable error tends to make the results appear rather more accurate than the standard error". Moroney28 stated (in 1951) that "the term 'probable error' was used in former times to denote 0.67450 (50 pct confidence using the normal distribution)....the term, a poor one, is now very much obsolescent. It has been said that 'it is neither an error nor probable' ". Bennett and Franklin in 1954" in discussing statistical confidence levels mentioned that "the customary use of the 5 and 1 pct levels is not completely a matter of chance; these levels probably represent a balance between the desire to be correct and the desire to be specific. Also in most people's minds the borderline between something that could possibly happen and something that is not likely to happen is somewhere in this region. Certainly 5 or 1 pct confidence limits are to be preferred to limits such as the 'probable error' which has only a 50/50 chance of including the correct value." It may readily be seen that the 95 pct confidence level, which is given by 1.960 (assuming large sample size), thus corresponds to approximately three times the "probable error". Indeed, limits of one standard deviation correspond only to about 68 pct probability. Even if we triple the tolerances given by the authors in the equations of their Table 111, the deviations do not become excessive and would not detract from their excellent results. It could then be said with a high degree of confidence (95%) that the precision of the slope and intercept values is about *3-5 percent of their absolute levels rather than the 1-2 percent implied in Table 111. This is then compatible with an earlier suggestion of Gokcen~' of a probable accuracy of 5 pct in dissolved oxygen measurements by the technique employed. Alternatively, the authors could have

Jan 1, 1967

Prospectors were digging silver in the Ray mine area in 1873, and by 1880 high-grade copper ore was feeding a 30-ton copper furnace. In 1910, D. C. Jackling and his associates organized the Ray Consolidated Copper Company, known in mining circles as Ray Con, to exploit the Ray orebody. For 50 years, all mining was underground and the Ray mine was known the world over for innovations in mining methods. It was the first to mine important tonnage (8,000 tpd) by block caving methods. The mill at Hayden, 26 miles (41.6 km) from the mine, kept pace with the new mining methods developed at Ray and in the early 1920's flotation replaced gravity concentration by the vanner machines. First mining by open pit methods began in 1950 and in January 1955 all underground mining was discontinued. The new primary crushing plant, installed in early 1967, featured design simplicity with a low capital cost. The 54 in. gyratory crusher was installed within a total height of 6 1 ft (18.65 m) from the truck dump road bed to the floor beneath the feeder-conveyor under the surge pocket. The crusher is fed by 120-ton trucks dumping from one side only into a 200-ton hopper equipped with a horizontal splitter bar to protect the crusher spider. The crushed ore pocket, of 120 -ton live capacity underneath the crusher, discharges to a 0 to 200 fpm (61.2 mpm), variable-speed, 72 in. by 80 ft long (1.83 m by 24.4 m) sloped belt feeder, probably a first in the industry. Wood-picking stations are provided on either side of the belt so that old mine timbers and tramp iron can be removed from the crushed ore and the wood can be dropped into Dempster containers located below the belt. Counter-weighted finger gates control the bed depth on the belt at 14 in. (356 mm) and a low- level radiation unit automatically maintains a minimum of a 3 ft bed (900 mm) of material on the belt directly under the surge pocket. The conveyor is skirted for its full length and is approximately 60 in. (1.52 m) wide inside its metal skirt liners. Ten impact idlers at 12 in. (305 mm) spacing are provided under the loading pocket and remaining idlers are spaced at 18 in. (457 mm). The belt is 1 ¼ in. (31. 8 mm) thick; and, while it has occasionally been damaged by tramp material, belt life averages 11 million tons. When the belt is changed, the coiled new belt is lowered into position onto one of two belt stands mounted over the feeder, the old belt is cut, and one end is attached temporarily to the new belt. The other end of

Jan 1, 1978

By C. S. Barrett, D. F. Clifton

THE transformation that occurs in lithium and its solid solutions containing magnesium1,2 is similar in many respects to other diffusionless transformations of the martensitic type. This general similarity makes it desirable to investigate the transformation curves in detail. The current interest in the phenomenon of stabilization in martensitic transformations has created a need for a careful appraisal of possible stabilization effects in both cooling and heating transformations in lithium alloys. The effect of prior heat treatment on the temperature at which transformation begins and the effect of various temperature cycles in partially transformed alloys also merit attention. Limited data on some of these features were presented previously,' but the present studies have been made with improved apparatus, in which erratic fluctuations were smaller than in the earlier work, and include many independent determinations of certain critical observations. Material and Methods Geiger counter X-ray spectrometers were used: a Norelco instrument, original model, and a General Electric XRD-3. The low-temperature specimen holder has been described elsewhere." Specimens 10 mm in diam and 1.5 mm thick were held in firm contact with a copper block which was attached to the lower end of a stainless steel tube that extended up to a reservoir of liquid nitrogen. A heating coil on the tube permitted a controlled temperature gradient along the tube, so that desired temperatures and rates of heating and cooling could be obtained by controlling the heating current. The specimen was surrounded by an atmosphere of evaporated nitrogen in an insulated chamber having double cellophane windows. The temperature of the specimen was read by a thermocouple imbedded in it close to the irradiated area; the specimen could be held at constant temperature within 1°C for long periods. The body-centered cubic 200 reflection near 8 = 26" was used as the index of the amount of b.c.c. material present; occasional checks were made using the most suitable line of the low-temperature phase, the close-packed hexagonal 110 line near 8 = 29". Copper radiation was used throughout. A continuous record was made of the reflected intensities on a strip chart recorder, both when the peak intensity of a line was being followed and when the lines were being scanned at constant temperature. On the continuous recordings of peak intensity, periodic checks were made on the background intensity between the lines, and on the setting of the spectrometer for maximum intensity. The lithium-base solid solution containing 12.4 atomic pct Mg (33.3 wt pct) that had been used previously' was chosen, as it had a transformation range at relatively high temperatures, so as to permit wide temperature cycling within the range. Just prior to use a pellet was cut from the ingot,

Jan 1, 1951

By J. F. Haseman, J. E. Davenport

IN the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1-2 results in inadequate beneficiation. INVESTIGATION OF FLOTATION METHODS Flotation has been used in Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate.3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over-all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P205 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P205, 20; Si02, 40; CaO, 29; Fe203, 2; A1203, 3; F, 2.3. The particle-

Jan 1, 1947

By J. G. Giddings, R. Kobayashi

Residual viscosity, the ViSCOSitY at a given pressure and temperature minus the dilute gas viscosity at the same temperature, has been found to be independent of temperature for pure components and mixtures for simple molecules and light hydrocarbons. The residual viscosities for methane, ethane, propane and four mixtures were correlated as a function of reduced density and molecular weight. INTRODUCTION Earlier efforts in correlating the viscosity of light hydrocarbons and associated gases under pressure, primarily by some form of the corresponding states principle, have been reported elsewhere.7 The formal theory of corresponding states principle for viscosity from non-equilibrium statistical mechanical arguments for simple molecules has been developed by Helfand and Rice.13 The most serious obstacle to the development of a generalized corresponding states representation of viscosity data, even for simple molecules, has been the limited quantity of precise viscosity data of pure components and mixtures over a wide range of pressure and temperature conditions. Viscosity data on light hydrocarbons have recently been contributed by several laboratories.2,6,8,23,25,26 In the study of the viscosity of nitrogen, Michels and Gibson" observed that the viscosities of nitrogen as a function of density gave parallel isotherms. The same behavior has since been reported for other gases.".= The observed behavior indicates that the residual viscosity or the viscosity at a given pressure and temperature minus the dilute gas viscosity at the same temperature is a unique function of the density. Abas-Zade,1 Michels and Botzen,18 and Michels, Bot-Zen, Friedman and Sengers,19 observed similar behavior for thermal conductivity, the residual thermal conductivity being defined in a manner parallel to that of residual viscosity. Thodos and co-workers 4,15,24 applied the residual viscosity concept to the viscosity of pure monatomic and diatomic gases. Ellington and co-workers10,25 made the residual viscosity vs density plots for ethane and propane, but omitted the region below a residual viscosity of 15 micropoise and showed a systematic separation of the ethane isotherms in the low density region. Eakin correlated the residual viscosity of methane, ethane, propane and n-butane empirically as a function of density and molecular weight: Carmichael and Sage6 recently presented ethane residual viscosity vs density values in the gaseous liquid, and near critical regions as a single univariant function of density. Flynn, Hanks, Lemaire and ROSS" have contributed extremely accurate viscosity data to confirm that the residual viscosity concept is essentially correct, but may not be accurate within 0.1 per cent of the viscosity value for the gaseous state- The recent studies by Giddings12 indicate that the residual viscosity of methane, propane and each of four methane-propane mixtures are unique functions of density Over the temperature and the density ranges studied.

Jan 1, 1965

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By Harry C. Gatos, Frank J. Bachner, Mario D. Banus

The portion of the Nb-Sn phase diagram between 75 and 79 at. pct Nb at temperatures near the liquidus has been investigated by melting alloys of known composition and examining the microstmc-tzlres resulting when these melts were quenched. The Nb-Sn samples were contained in magnesia sleeves, and were mounted in a high-pressure apparatus. It was shown that Nb3Sn me1ts by a peri-tectic decomposition and that the composition of the compound Nb3Sn at the peritectic horizontal lies between 77 and 78 at. pct Nb. Analysis of the phases present in the samples was accomplished by anodic staining techniques and an electron-microbeam analyzer. DURING the past several years a great deal of work has been devoted to the Nb-Sn system, and the bulk of this work has been primarily concerned with the intermetallic phase Nb3Sn. However, the melting characteristics of Nb3Sn have not been investigated because of the difficulty in maintaining known compositions due to tin losses by vaporization, and the added difficulty of containing Nb-Sn alloys without sample-container reaction at the high temperatures involved. This paper reports on the development of a technique for containing Nb-Sn alloys under pressure high enough to prevent tin losses at temperatures in excess of the liquidus. Using this technique, melts of known composition were made and a phase diagram near the liquidus is proposed based on the microstructures resulting when these melts were quenched. EXPERIMENTAL The Nb-Sn alloys weighing 0.7 g each were prepared in the form of cylinders. Niobium powder, -200, +325 mesh, and tin shavings with a minute amount of tin powder for a binder were mixed in the desired proportions and cold-pressed at 50,000 psi in a 0.150-in. die. This cylinder was then enclosed as shown in Fig. 1, and the entire arrangement mounted in a 2.6-in. pyrophyllite tetrahedron.' The desired temperatures (-2500°C) presented several problems in high-pressure container materials. Boron nitride, the usual sample holder, was found to react with niobium to form the nitride. However, MgO cans and plugs machined from refractory rods did not melt nor react with the sample. Thick tantalum contact disks were used to carry the large currents (~450 amps) to the graphite heater, since tantalum did not melt and had enough strength to prevent extrusion of the sample. It was further observed that the graphite heater and tantalum disks could not be in direct contact with the pyrophyllite because it melts and decomposes at these temperatures to kyanite and coesite (SiO2),2 the former reacting with graphite and the latter with tantalum to form the silicide. The use of a MgO outer sleeve

Jan 1, 1965

By F. W. Glaser

Iron-silicon alloys have had a great influence, in many ways, in modern industry. Silicon steels have been used almost exclusively for the construction of electrical machinery, but have also become an important material for structures which benefit by the high tensile and yield strengths of this material. In elaborating on the early history of work done on iron-silicon alloys, Greiner, Marsh and Stoughton1 went back as far as 1808, and pointed to Berzelius as the first producer of ferrosilicon. During the last twenty years some very important contributions in the form of studies of the iron-silicon system, as well as of the physical properties of these alloys, have been published. In consideration of the brit-tleness and poor machinability of alloys containing more than 5-6 pct Si, commercial interests have stimulated the research done on iron-silicon alloys, but mainly in the range of 0 to 6 pct Si. Yensen2 has shown the influence of im- purities, such as carbon, sulphur and phosphorus on the magnetic properties of 2, 4, and 6 pct Si alloys. Corson3 extended his investigation of physical properties to approximately 32 pct Si, and attributed the brittleness of the high-silicon material to the particular constitutional features of the alloys. Though mentioned earlier in the literature, the effect of nitrogen on crystal growth and magnetic permeability of iron-silicon alloys has been demonstrated recently by Morrill4 and Rostoker,5 respectively. In all the above quoted investigations, except that of Rostoker,5 sand or chill casting processes were employed for the preparation of samples. A major advantage of the powder metallurgy process is that it does away with time-consuming machining in many applications. The powder metal industry is always interested in pro- ducing a finished product employing a material which has presented considerably greater difficulties in manufacture by other methods. Steinit26 described preparation and testing of various Fe-Si alloys which were produced by the powder metallurgy process for the manufacture of armatures for small electric motors or generators. While Steinitz investigated alloys up to 6 pct Si, Rostoker5 went as high as 9 pct Si. The author7 previously discussed the diffusion of iron-silicon compacts containing 6 and 10 pct silicon. It is the object of this paper to study the progress of diffusion occurring in iron-silicon alloys by electrical resistivity measurements. All samples were prepared by pressing and sintering of compacts. Iron, silicon, and Fe-Si powders of various mesh size and compositions were employed to obtain test samples. It was assumed that complete diffusion had been obtained when the electrical resistivity reached a constant value characteristic for that particular alloy. To this end, electrical resistance measurements were used to follow the progress of alloying under various conditions.

Jan 1, 1950

By J. F Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By J. F. Haseman, J. E. Davenport

In the brown rock phosphate fields of Tennessee there are large deposits of phosphate matrix in which quartz is a major constituent of the gangue, and which cannot be beneficiated by the conventional washing process to yield a concentrate of suitable grade for use in the electric furnace. A huge tonnage of high-grade phosphate concentrate is produced in the Florida pebble district from low-grade siliceous feed. However, the characteristics of the low-grade siliceous Tennessee ore are such that flotation under the conditions employed in treating the Florida ore1,2 results in inadequate beneficiation. Investigation of Flotation Methods Flotation has been used in 'Tennessee primarily to produce a concentrate of premium grade by moderate enrichment of a marketable grade of phosphate. 3,4 A secondary use was to increase the recovery of phosphate from the fines (down to approximately 200 mesh) from medium-grade ores with a concomitant moderate increase in over all grade.3,5 It was considered desirable to investigate methods of improving the grade of washed products from low-grade siliceous Tennessee ore when these products were substantially below the requirements for use in the electric furnace. The present paper describes the results of a laboratory-scale study of factors that affect the beneficiation of such siliceous phosphate ore by flotation. The primary objective of the investigation was to ascertain the conditions under which the ore could be made to yield a concentrate suitable for reduction in the electric furnace. It was assumed that a phosphate concentrate for electrothermal reduction should contain at least 26 pct P2O5 and should have a weight ratio of silica to lime of not more than 0.80. Since a concentrate of moderate grade can be used in the electric furnace, and since, as Grissom4 has shown in detail, the ore will not bear the cost of expensive treatment, the study of collectors was limited to the relatively inexpensive fatty acids. A secondary objective was to determine whether a portion of the phosphate could be recovered in a grade suitable for treatment with phosphoric acid to produce 45 pct superphosphate. The ore consisted of variably cemented sand interlayered with clay. The sand layers were composed of grains of quartz, phosphate, and clay embedded in a matrix of clay and phosphate. Some clay was finely disseminated in the phosphate grains. Little massive high-grade phosphate was present. The material used in the flotation tests was a washed sand that had been separated from the ore in a bowl classifier at the TVA phosphate-washing plant. The percentage composition of the sand was as follows: P2O5, 20; SiO2, 40; CaO, 29; Fe2O3, 2; Al2O3, 3; F, 2.3. The particle-

Jan 1, 1948

By W. David Menzie

An inventory of the mineral resources of a region is a most desirable basis for planning their systematic development. In the absence of appropriate samples upon which to base a reliable estimate of this inventory, investigators have resorted to a number of indirect approaches; the unit regional value concept forms the basis for one such approach. The produced resources of a region are a function of the inventory multiplied by the degree of intensity (some fraction between zero and one) of development of the resources. A convenient means of expressing this amount is to accumulate the weight and value of resource and to prorate the totals over the area represented by the unit sampled; i.e., weight and value per unit area or tonnes/km.2 and U.S. 1967 $/km.2. When this approach is used for the U.S.A., South Africa and Rhodesia the average value of (log.) U.S. 67$/km.2 for the states of the U.S.A. and South Africa are similar ($55,176 U.S.$67/km.2 and $52,538/km.2 respectively); whereas, Rhodesia is relatively underdeveloped (10,301 U.S.67$/km.2). On the other hand if the individual commodities are used as a basis for comparison, the U.S.A. shows the greatest diversity (67 commodities out of a possible total of 75) with South Africa next (50 commodities) and Rhodesia last with only 26 commodities. Since it is known that area and value are not simply related perhaps diversity is directly related to area. Again the kinds of commodities which have contributed the greatest value to the totals differs, with fuels (petroleum, coal and natural gas) predominating in the U.S.A. totals; whereas, South Africa and Rhodesia obtain their greatest contributions from gold, diamonds (S. Africa) coal and asbestos. In each case the greatest value of resources is produced from sedimentary rocks. As a somewhat different kind of example, consider a single resource (petroleum, the most valuable in the U.S.A.) over a large area (number of sampling units) the U.S.A. by state. Furthermore, assume that the model frequency distribution of the amount of petroleum (tonnes/km.2) is log normal. Then the present production fails to match the model first because 17 states (34% out of 50) have not produced petroleum. Of the remaining 33 states, Louisiana has produced the most (15,177 tonnes/km.2) and the frequency histogram is still skew. A spatial analysis of the distribution of the amount of petroleum by state shows that the samples (i.e., states) are not random; the non-producers and producers tend to cluster. It remains to be seen if this is indeed a true representation of the incidence of petroleum or is a function of the exploration philosophy currently in vogue.

Jan 1, 1977

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

Aluminum has been found to be soluble in a titanium to about 26 pct, and to raise the temperature range of transformation from a to 8. Two intermediate phoses exist in the system, a new face-centered tetragonal phase, designated as 7, which occurs between 34 and 46 pct Al, and TiAI Metallographic and X-ray diffraction data were used to determine the diagram. ALUMINUM is one of the useful alloying additions for titanium-base alloys. It is an important constituent in two commercial alloys released in 1950, one containing 4 pct A1 and 4 pct Mn, and the other containing 3 pct A1 and 5 pct Cr as the metallic alloy content. It is probable that, in the future, other titanium alloys containing aluminum will be released. In the course of alloy development work, some of the features of the constitution of titanium-rich Ti-A1 alloys have been developed. These are described in the present paper. The only available information on the Ti-A1 system concerns the aluminum-rich end of the diagram. In summarizing the early work, Hansen' indicated that there is little solubility of titanium in aluminum, and that a two-phase region exists up to the intermediate compound, TiA1a (37.2 wt pct Ti), which has a congruent melting point at 1355°C. Fink' has reported that a peritectic reaction occurs at 665°C between the melt and TiA1³ to form the terminal solid solution of titanium in aluminum. The solubility of titanium in aluminum has been established at 0.24 pct at 510°C and is estimated to be between 1 and 1.5 pct at the peritectic temperature. No information has been published on the diagram above TiAl,, other than a statement- hat aluminum raises the a to ß transformation temperature of titanium. Materials and Preparation of Alloys Iodide-type titanium and high-purity aluminum were used in this investigation. Typical analyses of these materials are given in Table 1. Alloys were prepared by arc melting on a water-cooled copper hearth, using the techniques described previously for contamination-free melting.' Weight losses during melting were very low, ranging from 0 to 0.02 g in a 10 to 15 g charge, indicating that little or no loss of aluminum occurred during melting. This permitted the use of nominal compositions for these alloys. Alloy ingots containing from 0 to 7.5 pct A1 were rolled in air at 850°C to 0.040 in. sheet. Alloys containing from 7.5 to 16 pct A1 could only be rolled about 25 pct reduction at temperatures up to and including 1200°C. Alloys containing above 16 pct A1

Jan 1, 1952

By E. A. Gulbransen, W. S. Wysong

The behavior of molybdenum and its surface oxides in oxidizing and reducing gas atmospheres and in high vacua at elevated temperatures is a question of scientific and technical importance. The use of molybdenum as a metal or as an important component in alloys in oxidizing atmospheres at elevated temperatures has been limited because of the unprotec-tive nature of its oxide film and the volatility of this oxide at moderate temperatures. This communication will present results of a vacuum microbalance studyl, 2 of the following problems: (I) the oxidation kinetics in the temperature range of 250°to 450°C; (2) the reduction with pure hydrogen of thin oxide films formed on molybdenum; (3) the volatility of the thin oxide films; and (4) the vacuum oxidation of molybdenum at high temperatures. Molybdenum is an interesting metal to study for the following reasons: (I) although the oxide-to-metal-volume ratio is greater than one, the metal is not considered protective; (2) the metal oxidizes readily at temperatures of 2 50°C and higher; (3) the oxides of the metal are reduced at temperatures as low as 500°C by pure hydrogen; (4) the oxide Moo3 melts at 795°C; and (5) the oxides of molybdenum are volatile at moderate temperatures. The following variables are studied in the oxidation kinetics: time, temperature, pressure, surface preparation, surface area, concentration of inert gas in the lattice, cycling procedures in temperature, vacuum effect and high temperature vacuum oxidation. The general interpretation of many of these factors has been previously discussed. Literature The oxidation of molybdenum has not been studied critically. Although many studies have probably been made on the kinetics of the oxidation process, none has been reported in the literature available to us. The crystal structures found in the oxidation of molybdenum have been studied by Hickman and Gulbransen." Their results showed that Moo2 is the oxide which is stable in contact with the metallic substrate throughout the temperature range 300 to 700°C. As the film thickens in the low temperature range, MoO3 becomes predominant on the surface. Above 400°C, Moos is no longer observed, MoO2 being the only oxide found. Hagg and Magneli6 have shown from an X ray study that the a-phase, orthor-hombic Moo3 is stable up to 1050°C. Two other phases, ß and ß with compositions close to MoO2.90 are also obtained. The formula for the 0 phase is not given but that of the ß phase is defined as Mo9O26 The 0' phase is found to be built upon a monoclinic unit cell. A ?-phase is isolated from a preparation MoO2.75 heated for 17 hrs at 670°C. This phase is

Jan 1, 1949

By R. D. Pehke, J. F. Elliott

The solubility of nitrogen in liquid pure iron has been measured as a function of pressure and temperature. Sieverts' Law is obeyed at all pressures up to 1 atm and the temperature coefficient of solubility is 8 x 106 %/°C. The solubility of nitrogen in liquid iron alloys has been studied by the Sieverts' method and by the sampling method. The solubility is decreased by Al, C, Co Cu, Ni, 0. Si atzd Sn, and it is increased by Cr, Cb, Mn, Mo, Ta, W, and V. Interaction coefficients eN, for the effect of these elements on nitrogen dissolved in liquid iron, are reported. 1 HE effect of nitrogen upon the properties of steel may be desirable or not, depending upon the composition, processing treatment, and the use of the product. To understand the behavior of nitrogen in the various steelmaking processes, it is necessary to have reliable fundamental data pertaining to the solubilities, rates of solution, and chemical reactions of nitrogen in steel, particularly in the liquid state. In an effort to extend our knowledge in these areas, an investigation of the thermodynamics and kinetics of the solubility of nitrogen in liquid iron alloys was undertaken. The thermodynamic aspects of the study are presented in this paper. The solubility of nitrogen in liquid pure iron has received the attention of several investigators whose results are summarized in Table I. Reasonable agreement among the more recent researches1-l8 is found for the solubility of approximately 0.044 wt pct at 1600°C and 1-atm pressure of N,, for the temperature coefficient of solubility being small but positive, and for adherence to Sieverts' law for pressures up to 1 atm. The solubility of nitrogen in a number of binary liquid iron alloys has been studied: Fe-A1,3 Fe-As,16 Fe-C,3, 71 18, 19, 20 Fe-Cr ,5,7, 10, 11, 15 21 Fe-Co,'4, '6 Fe-Cu,'6 Fe-Mn,10, 11, 18 Fe-Mo,13, 16 Fe-Ni,10, 11, 13, 15, 16 Fe-O,16, 17, l9 Fe-p,7 Fe-S,l6 Fe-Sb,16 Fe-Se,lg Fe-Si,4) 97 '77 187 19>2° Fe-Sn,16 and Fe-v.51 '3 A few ternary systems have been studied, most of which were reviewed by ~angenberg" who applied the methods suggested by WagnerPz3 Chipman,24 Darken and G~rry, and Morris and Buehl26 for predicting solubilities in multicomponent alloys. Langenberg22 and Humbert and Elliott15 compared the solubilities computed from simple binary alloy systems with experimental measurements of nitrogen solubilities in liquid iron containing two or more alloying elements. The interaction coefficients for nitrogen in

Jan 1, 1961

By R. I. Jaffee, H. P. Nielsen

In recent years much attention has been given to high melting alloy systems. It has been of interest in this respect to investigate the alloys of platinum and tungsten, which were known from the literature to have very high melting points up to about 50 pct tungsten, but about which little had been published on the high-tungsten side of the system. Powder metallurgical methods were used throughout this investigation for the preparation of the alloys, utilizing electrical sintering techniques such as are used for tungsten and molybdenum. In the course of the work it was found desirable to determine fusion temperatures of the alloys, and it was possible from these and other data to draw a tentative constitutional diagram (solidus, mostly) applicable to the high-temperature part of the system. No attempt was made to determine solid solubility vs. temperature data, nor to investigate the lower temperature transformations in the solid state. Data on the microstructure, hardness, and a note on oxidation resistance of the sintered alloys were obtained. Past Work Miillerl determined liquidus temperatures of platinum-rich alloys to 50 pct tungsten, using a radiation method employing a photoelectric cell, and found that the melting points increased progressively from I771 C for platinum to 2350°C for the 50 pct alloy. Microscopic evidence by Miiller that complete solid solutions exist to 50 pct tungsten was not checked by Kremer2 who, according to Vines and Wise,3 found that "although the 8 pct tungsten alloy was a solid solution, the 26 pct tungsten alloy contained a eutectic or an intermediate phase." Hultgren and Jaffee4 using X ray methods found continuous solid solutions to at least 33.6 pct tungsten (35 at. pct) after annealing in vacuum for 6 days at I000 C. Vines and WiseS report work communicated to them by E. C. Rhodes on wrought alloys to 7 pct tungsten, which showed that tungsten hardened platinum extremely rapidly, and was one of the most potent hardeners of the binary additions to platinum. Considerable quantities of 4 pct tungsten platinum wire have been produced for grids in radar tubes and for aircraft spark plugs. Some of the alloy for the latter application is made by sintering, the remainder by smelting and casting. Materials The platinum powder used in this work was kindly supplied by the Research and Development Laboratory of the Owens-Corning Fiberglas Corp., Newark, Ohio. It was prepared from scrap platinum. After dissolving in aqua regia and evaporating almost to dryness, the solution was worked up several times with concentrated HC1. The resultant platinic chloride was diluted considerably, and metallic zinc was added, which precipitated the platinum in a very finely divided form. After dissolving the

Jan 1, 1949