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THE increased demand for titanium alloys with improved high-temperature creep strengths has stimulated interest in silicon as an alloying addition to titanium. Silicon is a potent solid-solution strength-ener and, if added in sufficient concentration and properly heat-treated, can also dispersion-strengthen titanium by eutectoid decomposition.' However, better understanding of the nature and distribution of the resulting silicide dispersion in more highly alloyed titanium matrices is necessary for the development of useful titanium alloys which utilize the latter strengthening mechanism. This note describes the chemical and crystallographic characteristics of the silicide phase as it occurs in a typical high-temperature near-a titanium alloy matrix. Several Ti-6A1-3Sn-3Zr a11oys containing various amounts of silicon ranging from 0.1 to 1.0 pct were melted as 10- to 20-lb ingots and processed into 1/2-in.-diam bar stock. The microstructures of specimens annealed at various temperatures were conveniently summarized by the (Ti-6Al-3Sn-3Zr)-Si pseudobinary phase diagram illustrated in Fig. 1. Comparison with the Ti-Si equilibrium diagram indicates the substitutional solutes (Al-Sn-Zr) increase the eutectoid temperature and decrease the a terminal solubility. Annealing at temperatures sufficiently high to dissolve the silicon in a ß solid solution and cooling rapidly enough to preclude coarsening generally produced a uniform dispersion of fine silicide particles, whereas annealing at temperatures near but below the ß transus produced relatively coarse silicide particles. Annealing in the limited a, plus 3 region produced a duplex coarse and fine silicide array. Several a-annealed specimens were examined by X-ray diffraction to determine the crystallographic identity of the precipitate phase. Copper Ka X-ray diffraction patterns of bulk specimens which contained 0.5 and 0.8 pct Si were virtually identical to that of the silicon-free Ti-6Al-3Sn-3Zr base alloy except for a slight shift in some of the high-angle diffraction lines. Apparently the silicide volume fraction was too low to be detected in bulk specimens. X-

Jan 1, 1969

By P. Ramachandraraa, T. R. Anantharaman

THE technique developed by Duwez, Willens and Kle-ment' for rapid solidification of molten alloys in small quantities by ejecting them on to a highly conducting substrate with the aid of a shock wave has come to be known as "liquid quenching" or "splat cooling" in literature and has already been applied to alloys of many binary systems.' The very high cooling rates of the order of l060 to 1080 per sec obtained in this technique and the consequent drastic undercooling of the melt have led to such striking results as formation of new amorphous and crystalline metastable phases and extension of solid-solubility limits in many alloy systems. The cooling rates in these experiments can, however, be neither accurately measured nor effectively controlled and hence the occurrence of either more than one metastable phase or appreciable differences in constitution in splat-cooled alloys of the same composition cannot be ruled out.3 In fact, workers in two laboratories have reported formation of two different cubic metastable phases in liquid-quenched Au-Si alloys containing 17 to 20 at. pct si.4,5 The present note deals with some new and interesting results obtained in a Ag-21 at. pct Ge alloy and a Au-27 at. pct Ge alloy subjected to the liquid-quenching treatment at different cooling rates. Two alloys of nearly the same composition had earlier been rapidly solidified by the standard "gun technique" in the same laboratory and shown to solidify in nonequilibrium structures, viz., an hcp phase (a = 2.987Å;c =4.718Å) in the Ag-Ge system6,7 and both hcp (a = 2.885Å; c = 4.754Å) and tetragonal (a = 11.627A; c = 22.491Å) phases in the Au-Ge system.3 Apart from different substrates (copper and stainless steel), different melt temperatures (50º to 500°C above the liquidus), and different capillary sizes (0.4 to 1.5 mm diam) in the "gun technique", slower cooling rates of the order of l050C per sec were also obtained in the present work by replacing the substrate by water at room temperature in a modification of the technique due to Olsen and Hultgren.8 No attempt was made to measure the cooling rate in any experiment. The products varied from fine powder (>40 pct by wt—200 mesh) obtained by quenching in water to thin flakes and foils (11.0 sq mm to 4.0 sq cm) produced by splat cooling. They were subjected to the Debye-Scherrer method of X-ray examination in each case. In case of the Ag-Ge alloy, in addition to the expected metastable hcp phase,6 a coexistent tetragonal phase (a = 5.093,Å; c = 7.009Å) was detected in some experiments. Eight weak X-ray reflections from this phase could be identified, two of them being the same as reported earlier.7 With increase in the cooling rate, the dominant hcp phase seems to be first accompanied by traces of silver or germanium and then either homogeneous or mixed with traces of this new tetragonal phase. The splat-cooled Au-Ge alloy showed generally the expected hcp and tetragonal phases,3 but sometimes traces of germanium were also present. Further, two new tetragonal phases with the following lattice param ters could be clearly identified in samples quenched

Jan 1, 1970

By P. S. Rudman

Crystal-structure occurrences in binary phase diagrams of fifth- and sixth-period elements, zirconium through palladium and hafniun through platinum, are surveyed with the conclusion that average .group number GN is the dominant correlative. This is interpreted in terms of curves of enthalpy differences between competitiue structures that are continuous func -tions of GN. It is further reasoned that the absolute formation energies may also be continuous functions of GN and if so can be simply obtained from the regatives of the heats of sublimation of the elements. It is shown that from such a heat of formation-GN plot the heats of mixing of alloy systems can be quantitatively predicted. For example, for sixth-period alloys very large exothermic heats of mixing are predicted for systems that span GN = 6 (i.e., Hf-Pt, Ta-Os, ...). Thermodynamic data with which to test these predictions do not appear to be available. If in the latter transition (A subgroup) elements we eliminate from consideration the fourth period where magnetic terms contribute to crystal-structure stability, as shown in Table I, there is a very regular sequence of structures. Using the group number (GN) assignments of Table I, which differ from the usual assignments of 8 to the elements listed as 8 through 10, it is perhaps trivial to say that the phase occurrence is a unique function of GN. However, the interesting aspect of alloys from among these elements is that the alloy structures also appear to correlate with GN. The GN for an alloy is given as GN = SixiGNi, where xi and GNi = atomic fraction and GN of component i, respectively. It is difficult to credit anyone in particular with having discovered this correlation, so many people have implicitly or explicitly employed it in the last 10 years. However, Bloom and Grant' in their correlation of s-phase occurrence with total number of d + s electrons were certainly one of the first to appreciate the correlation and Hume -Rothery2 appears to be responsible for the use of average GN as defined above. Only in the last few years have the phase diagrams of enough alloy systems been determined for this correlation to be surveyed with any degree of completeness. We shall here, in an abbreviated format, summarize the available phase-diagram literature and discuss some consequences of the GN correlation. BINARY DIAGRAM SURVEY In Figs. 1 to 3 the phase occurrences are summarized. In Fig. 4 the occurrence limits for the more common structures are summarized. That the GN of an alloy falls within the occurrence limits of a particular structure is a necessary but not a sufficient condition for the appearance of that structure. The preceding figures certainly illustrate that GN is a dominant correlative for structures of these elements. Many of the diagrams have complications, with ordering and other phase changes occurring in intermediate phases, that cannot be clearly accommodated in such a schematic survey and have hence been left out. Such omissions cannot, however, negate the GN correlations discussed here. Relative atomic size is also an important crystal-structure determinant and since atomic size varies quite regularly with GN for these elements it is possible that the apparent GN correlation is basically a size correlation. In Fig. 5 relative size occurrence limits are given for intermediate phases and extended terminal solutions. The relative volume, ?v/(v) - 2(vA - vB)/(vA + uB), has been taken as the measure

Jan 1, 1968

By L. J. Howell, H. H. Kellogg

AN a previous paper' the phase diagram and vapor pressure of melts in the systems NaC1-ZrCl,, KC1-ZrCl,, and NaC1-KC1 (1:1 molar)-ZrC1, were reported. This note supplements the earlier paper with the results of electrical conductivity measurements on NaC1-ZrC1,and NaC1-KC1 (1:l molar)-ZrC1, melts. The design of the conductivity cell is shown in Fig. 1. Tungsten electrodes, A, were sealed into the Pyrex cell, C. That portion of the electrodes in contact with the melt was covered with a tight-fitting platinum cap. The electrodes were sur-

Jan 1, 1960

By Frank Foote, E. R. Jette

Precision lattice-constant measurements have been widely used in the study of cubic solid solutions but as yet have been rarely applied to noncubic solid solutions. (See, however, references I and 2.) With the high precision at present attainable in the measurement of lattice constants, the X-ray method should be readily applicable to noncubic solid solutions. In the work reported here, hexagonal close-packed magnesium was used as the solvent and either lead, bismuth or gold as the solute. In the magnesium-lead and magnesium-bismuth systems the a and c lattice constants were determined as a function of composition, densities were calculated from these lattice-constant data, these theoretical densities were compared with those directly measured and the solid solubility limit was determined on quenched specimens over a considerable range of temperature. In the magnesium-gold system, the solid solubility is very small but we have obtained an indirect check on the solubility limit previously reported. Materials and Preparation oF the Alloys The magnesium used was obtained from the Aluminum Company of America and was 99.987 per cent pure. Impurities as reported On the label were: Fe, Al, 0'004 per cent; Si, 0.009 per cent; Zn, trace; Cu, Pb, nil. The bismuth was Merck's analytical grade, minimum purity 99.95 per cent. Maximum impurities as listed on the label were: Fe, 0.008 per cent; Pb, 0.010 per cent; Ag, 0.010 per cent; Cu, 0.005 per cent; Sn, 0.003 per cent; Sb, 0.00; As, 0.000; S, 0.01 per cent. The gold was purified by double precipitation with sulphur dioxide. The lattice constants of these three metals have been previously reported.3 The lead used was test lead, silver free and with a maximum of 0.10 per cent heavy metal impurities. The lattice constant 01 this lead has been measured and found to be 4.94057 ± 0.00016 at 25°C. The alloys were prepared by melting together weighed amounts of the constituent metals in magnesia-lined alundum crucibles under an atmosphere of hydrogen purified by passing over magnesium heated to 500°C. The magnesia lining prevented contamination 01 the alloys with aluminum. Vacuum melting could not be used because of the volatility of magnesium. A high-frequency induction furnace was used for the melting operation and the stirring action of the current resulted in thorough mixing of the constituents. The melts were allowed to freeze in the crucible, the ingots obtained weighed about 10 grams. An extremely thin white film formed on the surface of the melts, sometimes covering only a part of the exposed surface. The ingots were filed clean, placed in small iror crucibles with close-fitting lids and indi. vidually sealed into Pyrex glass tubes Before sealing off, the tubes were alter

Jan 1, 1941

By Frank Foote, E. R. Jette

Precision lattice-constant measurements have been widely used in the study of cubic solid solutions but as yet have been rarely applied to noncubic solid solutions. (See, however, references I and 2.) With the high precision at present attainable in the measurement of lattice constants, the X-ray method should be readily applicable to noncubic solid solutions. In the work reported here, hexagonal close-packed magnesium was used as the solvent and either lead, bismuth or gold as the solute. In the magnesium-lead and magnesium-bismuth systems the a and c lattice constants were determined as a function of composition, densities were calculated from these lattice-constant data, these theoretical densities were compared with those directly measured and the solid solubility limit was determined on quenched specimens over a considerable range of temperature. In the magnesium-gold system, the solid solubility is very small but we have obtained an indirect check on the solubility limit previously reported. Materials and Preparation oF the Alloys The magnesium used was obtained from the Aluminum Company of America and was 99.987 per cent pure. Impurities as reported On the label were: Fe, Al, 0'004 per cent; Si, 0.009 per cent; Zn, trace; Cu, Pb, nil. The bismuth was Merck's analytical grade, minimum purity 99.95 per cent. Maximum impurities as listed on the label were: Fe, 0.008 per cent; Pb, 0.010 per cent; Ag, 0.010 per cent; Cu, 0.005 per cent; Sn, 0.003 per cent; Sb, 0.00; As, 0.000; S, 0.01 per cent. The gold was purified by double precipitation with sulphur dioxide. The lattice constants of these three metals have been previously reported.3 The lead used was test lead, silver free and with a maximum of 0.10 per cent heavy metal impurities. The lattice constant 01 this lead has been measured and found to be 4.94057 ± 0.00016 at 25°C. The alloys were prepared by melting together weighed amounts of the constituent metals in magnesia-lined alundum crucibles under an atmosphere of hydrogen purified by passing over magnesium heated to 500°C. The magnesia lining prevented contamination 01 the alloys with aluminum. Vacuum melting could not be used because of the volatility of magnesium. A high-frequency induction furnace was used for the melting operation and the stirring action of the current resulted in thorough mixing of the constituents. The melts were allowed to freeze in the crucible, the ingots obtained weighed about 10 grams. An extremely thin white film formed on the surface of the melts, sometimes covering only a part of the exposed surface. The ingots were filed clean, placed in small iror crucibles with close-fitting lids and indi. vidually sealed into Pyrex glass tubes Before sealing off, the tubes were alter

Jan 1, 1941

By J. F. Butler

The degree and type of carbide dispersion resulting from changes in the cooling rate from austenite determine the amount of carbon remaining in solution after slow cooling- from a subsequent subcritical annealing treatment. A difjusion model has been proposecl to explain the effect of carbide dispersion on the amount of carbon retained in solution and the amount of carbon in solution has been related to the degree of carbon strain aging. COTTRELL and Leak' have shown that the rate of strain aging in low-carbon steels is dependent upon the amount of carbon and nitrogen in solution. Carbon can be effectively removed from solution as Fe , C by quench aging at temperatures of 200" C or lower; however, the relatively higher solubility of nitrogen at these temperatures prevents sufficient removal of nitrogen as iron nitrides. For this reason, nitrogen in solution has been considered the major cause of strain aging in rimming grades of commercial low-carbon steels. Nitrogen can be effectively removed from solution and nonaging steel produced through the addition of aluminum to form the stable nitride, AlN; however, the aluminum also causes deoxidation resulting in a killed steel. III an attempt to produce a rimmed steel which was also nonaging, Morgan and Shyne 2 investigated tile strain-aging properties of low-carban steels containing boron and found that strain aging was suplx-essed in steels containing as little as 0.007 pet B. The original purpose of this investigation was to determine the mechanism of strain-aging suppression by boron. Early in the study, the function of boron was discovered to be much like that of aluminum in that the formation of a nitride, BN, removed the nitrogen from solution.' However, during the course of the investigation, an effect of heat treatment upon the strain-aging properties and the amount of carbon in solution was found which could be related to the microstructure of the steel. The purpose of this paper is to examine these relationships among heat treatment, microstructure, carbon in solution, and strain aging in steels where nondetectable amounts of nitrogen are present in solution. EXPERIMENTAL PROCEDURE The investigation was carried out using 0.030 in. by 12. in wire specimens which had been cold swaged and drawn to the final diameter. Table I lists the compositions of the low-carbon steels used. Those with 'V' designations were vacuum melted and cast; the alloys designated 'AISI' were prepared from high-purity iron obtained from the American

Jan 1, 1962

By E. Marburg

Most ingots complete solidification vertically rather than transversely. This conclusion is based on complete solidification patterns of big-end-up and big-end-down ingots developed from dumped and split ingots. New mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon adequate width of vertical core. A LTHOUGH it has long been recognized that the A internal soundness of ingots is principally been recognizedthatthedependent on the process of solidification, knowledge of this process is still only fragmentary. The mechanisms causing the several types of segregation in ingots, which mechanisms are necessarily related to the solidification process, are not well understood. In absence of a better conception of the solidification process, it seems hardly surprising that mold design varies widely. Guiding principles for mold design are needed. At stake in the improvement of ingot quality are not only improved properties of steel but also appreciably higher yields of sound steel, which would considerably decrease manufacturing costs. In the present study, following a general description of the several types of segregation in ingots, Fig. 1, complete solidification patterns of a big-endup and a big-end-down ingot, including the zones of accelerated solidification, have been reconstructed. In both ingots, a core of vertical solidification extends from the base cone to the hot-top junction. Based on the finding that ingots complete solidification vertically rather than transversely, as has been previously assumed, new mechanisms for segregation in ingots are proposed. Internal soundness in ingots is found to depend upon the width of the vertical core, which in turn depends principally upon the width to height (w/h) ratio of the ingot. Solidification patterns of ingots are of three general types: 1—those in which vertical solidification does not reach the top, 2—those in which vertical solidification just reaches the top of the ingot, and 3—those in which vertical solidification reaches the top some time before transverse solidification would reach the middle of the ingot, so that a vertical core of definite width at the top of the ingot is developed. Axial defects vary characteristically with the solidification pattern. Examples of ingots of each type are presented. Dumped ingot data reported by Nelson' have been used in developing families of curves of transverse and vertical solidification, and in deriving the effect of the w/h ratio upon the solidification pattern. Photographs of many ingots split at Homestead and at Duquesne Works, United States Steel CO., as well as those published by the British Iron and Steel Institute,' have been studied and analyzed. In the interest of brevity, only typical ingots of each type or classification from the above sources have been reproduced. Segregation in Ingots Segregation in ingots falls into three principal classifications: 1—lamellar segregation, as revealed in sulphur prints (Figs. 2 and 3); 2—zone segregation, or broad variations in composition; and 3— interdendritic, or microsegregation. The last class, of minor importance, is not considered here. When liquid metal cools, according to the theory of differential or selective solidification,2 metal of relatively high purity selectively solidifies first. Liquid segregates (principally carbon, phosphorus,

Jan 1, 1954

By Alexandre Pourcel

The phenomena of liquation in steel or iron ingots of all sizes, but naturally to greatest extent in the heaviest ingots, have been noticed ever since the commencement on a large scale of the Besse mer and open-hearth manufactures; but they have been studied with care during the last few years only. The English and the Ameri cans were the first to publish the results of investigation upon phe nomena of this clam, to which they have given the name of segregation. Historical. Passing by that which has been written concerning the segregation observed in gray pig-iron, of which instances were given by Karsten, we shall confine ourselves here to that which is known of this subject with exclusive reference to ingot steel and iron. Mr. H. M. Howe, of Boston, in his Metallurgy of Steel, the most complete and well-arranged treatise upon steel, gives a resume of observations, with the results of numerous analyses, bearing upon the phenomena of segregation. According to Tchernoff (with whom we discussed this question at length in 1878, in connection with the cast-steel plates of large dimensions designed for the Italian fleet, which we showed him at Terre-Noire), Kalakoutsky called attention in 1866 to the lack of homogeneity in Bessemer ingots, especially when cast in sand. Our own attention had been called to the phenomena of liquation in 1868 by a somewhat surprising fact which appeared in almost every one of a number of steel-rail ingots coming from the works of Messrs. Pierre and Emile Martin at Sireuil, to be rolled at TerreNoire. In the heating or in the first groove of the rolls, a slice of from 6 to 10 centimeters (2.4 to 3.9 inches) separated itself from the head of each ingot. As a general consequence, the section of

Jan 1, 1894

By C. K. Eilerts

Finite difference equations were programmed and used to integrate the second-order, second-degree, partial differential equation with variable coefficients that represents the transient linear flow of gas-condensate fluids. Effect was given to the change with pressure of the compressibility factor, the viscosity, and the effective permeability and to change of the absolute permeability with distance. Integrations used as illustrations include recovery of fluid from a reservoir at a constant production rate followed by recovery at a declining rate calculated to maintain a constant pressure at the producing boundary. The time required to attain such a limiting pressure and the fraction of the reserve recovered in that time vary markedly with properties of the fluid represented by the coefficients. Fluid also is returned to the reservoir at a constant rate, until initial formation pressure is attained at the input boundary, and then at a calculated rate that will maintain but not exceed the limiting pressure. The computing programs were used to calculate the results that would be obtained in a series of back-pressure tests made at selected intervals of reservoir depletion. If effect is given to the variations in properties of the fluid that actually occur, then a series of back- pressure curves — one for each stage of reserve depletion — is required to indicate open-flow capacity and related flow characteristics dependably. The isochronal performnce method for determining flow characteristics of a well was simulated by computation. INTRODUCTION The back-pressure test procedurel is based on a derivation of the equation for steady-state radial flow of a gas, the properties of which are of necessity assumed to remain unchanged in applying the test results. The properties of most natural gases being recovered from reservoirs change as the reserve is depleted and pressures decline, and the results of an early back-pressure test may not be dependable for estimating the future delivery capacity of a well. The compressibility factor of a fluid under an initial pressure of 10,000 psia can change 45 per cent and the viscosity can change 70 per cent during the productive life of the reservoir. There are indications that the effective permeability to the flowing fluid can become 50 per cent of the original absolute permeability before enough liquid collects in the structure about a well as pressure declines to permit flow of liquid into the well. The advent of programmed electronic computing made practicable the integration of nonlinear, second-order, partial differentia1 equations2.3 pertaining to flow in reservoirs. Aronofsky and Porter4 represented the compressibility factor and the viscosity by a linear relationship, and integrated the equation for radial flow of gas for pressures up to 1,200 psi. Bruce, Peaceman, Rachford and Rice5 integrated the partial differential equations for both linear and radial unsteady-state flow of ideal gas in porous media. Their published results were a substantial guide in this study of integration of the partial differential equation of linear flow with coefficients of the equation variable. The computing program was developed to treat effective permeability as being both distance-dependent and pressure-dependent. In this study all examples of effective permeability are assumptions designed primarily to aid in developing programs for giving effect to this and other variable coefficients. The accumulation of data for expressing the pressure dependency of the effective permeability is the objective of a concurrent investigation. FUNDAMENTAL DIFFERENTIAL EQUATIONS DIFFERENTIAL EQUATION OF FLOW Linear transient fluid flow is represented by the partial differential equation,

Jan 1, 1965

By M. J. Pool, J. R. Guadagno

THE relative partial molar heats of solution in liquid tin have been determined for phosphorous, arsenic, and antimony at 750°K. This work was carried out as part of an over-all program to determine the heats of formation of the III-V semiconducting compounds. A differential twin-type liquid tin solution calorimeter was used in the investigation. All three elements are endothermic upon solution in tin. The relative partial molar heats of solution go through a minimum value at arsenic. No concentration dependence of the heat of solution was found in the dilute (0 to 2 at. pct solute) solution range investigated. The measured heat effects and the calculated relative partial molar heats of solution at infinite dilution are listed in Table I along with the relative heat contents of the solutes calculated from the data of kelley.1 All of the values are referred to 750°K even though the calorimeter temperature fluctuated by *1°K during the course of the experiments. In this range of temperature change no variations were found which were outside the experimental error. This would be expected since the partial molar heat of solution is in general a very insensitive function of temperature. The limits of error given in Table I represent the standard deviation from the mean. The reported error estimates only apply to the estimated precision of the data and not the accuracy. Systematic errors could be present which would affect the absolute values given. This is especially true in the case of phosphorous and arsenic where vaporization could occur. If this were true, the experimental values reported here would be too high and the true partial molar heat of solution would be less than that given in Table I. Moreover, the heat-content data could be in error and this would also affect the calculated values. The relative partial molar heat of solution of phosphorous at infinite dilution in liquid tin is given in Table I. This value is based on eight drops at

Jan 1, 1965

By G. W. Powell

G. W. Powell (Ohio State University)—Appleton and Bever measured the quantity Es which, for a solid torsion specimen, is basically an average quantity. Es is the amount of energy stored in a solid torsion specimen strained to a surface shear strain of divided by the total number of gram-atoms of alloy in the specimen. It would seem more meaningful and rigorous to deal instead with the quantity which is the energy stored per gram-atom of an alloy uniformly strained to the shear strain . The purpose of this discussion is to demonstrate that as a function of y is readily obtained from the torsion data. radius of the torsion specimen, shear strain at the surface of the torsion specimen density of the alloy, atomic weight of the alloy, and total energy stored in unit length of the torsion specimen. The energy stored in unit length of an elemental tubular section of the torsion specimen is, as given by Appleton and Bever, where E is expressed as calories per gram-atom. The energy stored in unit length of the torsion specimen is

Jan 1, 1963

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By D. W. Smith, C. H. Mathewson

In a series of papers published recently,' R. F. Mehl and associates have studied the characteristics of form and orientation of many segregate structures and have found diversified conditions which can be explained only by postulating some specific kind of cooperative mechanism permitting the matrix lattice in some favorable region to transform into the segregate lattice in an adaptable region presenting a geometrically similar arrangement of atoms. We have collected the published data on crystallographic relationships of this sort, chiefly derived from Mehl's work, in Table 1. It is evident at once that the crystal structure of the matrix does not uniquely determine the location of the plate structures or other forms assumed by the segregate. Thus, the first seven items in the table represent precipitation of platelike forms from a matrix of face-centered cubic structure, but these plates are found stratified along planes of form {1111, {loo), {110) or another unidentified form, depending upon specific conditions involving the nature and concentration of the segregating substance. Again, in a matrix of body-centered cubic structure, plates, needles or stars have been found and the favored inner surface of segregation may be a plane of form (110), (112), {210), or indeed a surface without crystallographic indices defining a bundle of close-packed lattice lines (strings of atoms) taken more or less at random. Such a surface might be formed ideally by revolving one of these parallel strings of atoms around another as an axis. Hanemann and Schroder2 recently discussed these questions, principally with relation to original conceptions concerning the process of

Jan 1, 1932

By V. R. Garfias, H. J. Hawley

FoR a number of years the senior author has been interested in the various geologic and engineering problems involved in the development of the petroliferous districts of northeastern Mexico, having in a previous paper* endeavored to present a summarized statement of the information relating to the geology and soil resources of this region. Of the many interesting geologic phenomena, perhaps those which have been the object of most speculation relate to the igneous intrusions which, in places, have a controlling influence on the accumulation of oil in commercial quantibies, a relationship which has been tentatively explained by various observers with as many interestingly different views. The authors of the present paper aim to record, in the course of a general discussion of the various viewpoints, some additional data, and present further tentative conclusions with a view to rounding out an up-to-date summary of the subject. The greater part of the area in question lies in the State of Vera Cruz, only a northwest fraction being in the State of San Luis Potosi. Vera Cruz is bounded on the north by the State of Tamaulipas, the northernmost of the Mexican States along the Gulf. The topography of the States of Tamaulipas and Vera Cruz and of Texas and Louisiana to the north, is controlled by the Gulf coastal plain which in northern Vera Cruz has an average width of about, 60 miles, the transitional topography between that of the rugged Banks of the Sierra and the lowlands of the coast being made up of a series of terraces and irregular hills and valleys. Geology and StRucture The greater part of the mainland of Mexico is made up of Tertiary and later effusive rocks and of sedimentaries of Cretaceous age. The igneous rocks form a belt from 150 to 300 miles wide, spurs of which shirt

Jan 1, 1918

By W. O. Philbrook, C. W. McCoy

The reduction of chromous oxide from lime silica alumina slags by carbon-saturated iron behaves as a first-order process having a rate of 0.001 grams Cr min 1 cm 2 (pct Cr ) , substantially independent of slag composition and temperature over an important range for iron smelting. The equilibrium ratio (pct Cr)/[pct Crl is below 0.04 for slags having lime-silica ratios above 0.6. MANY studies have been conducted on chromium in slag-metal systems under oxidized conditions. The Purpose of these investigations has been twofold; namely, (1) to determine those conditions which lead to greater chromium recovery in electric-furnace and open-hearth practice, and (2) to determine the nature of oxide inclusions and de-

Jan 1, 1959

By N. E. Rogen, N. J. Grant

AGE-hardening in nickel-chromium-titanium-aluminum alloys in the composition range characterized by the Nimonic alloys, is dependent upon the precipitation of the Ni3(AI,Ti) (y') phase.1 This phase is found to precipitate at about 700°C.1 Ni,Al is a face-centered-cubic ordered structure with a lattice parameter of 3.560 A. The atomic configuration is such that the aluminum atoms occupy the cube corners and nickel occupies the cube faces with titanium substituting for the aluminum preferentially. A maximum of three out of every five aluminum atoms can be replaced by titanium atoms in the -y 'phase.' When the solubility of the y'-phase is exceeded for titanium the T(Ni,Ti) phase is formed. The T-phase is an ordered close-packed hexagonal intermetallic structure which shows little solubility for the other elements in these alloys. The lattice parameter for T-phase is a - 2.5454 kr and c = 8.2900 kx units."

Jan 1, 1959

By R. H. Tien

The accuracy of the method of steady-state approximation applied to the problems of heat transfer involving phase change (London and Seban's solution) is improved by defining a "modified heat of fusion" which accounts for the effect of specific heat. An analytical expression for this modified heat of fusion is derived in terms of the actual heat of fusion, specific heat, and surface temperature. Numerical solution for the freezing of iron indicates that the ratio of the modified heat of fusion to the actual heat of fusion increases from 1.04 to 1.4 as the surface temperature decreases from 2700° to 1600°F. The heat transfer process accompanying solidification is complicated owing to the moving solid-liquid interface where the latent heat of fusion is released. Exact analytical solution is available only for a few special cases of freezing problems such as Stefan's1 problem. In a commonly used steady-state approximation method, London and seban's2 solution, the effect of specific heat is neglected. This approximation, however, may introduce some degree of error in mathematical analysis when the temperature of the solid surface is much lower than the freezing temperature, as in the case of freezing metals. In a recent work by Robertson and Schenck,3 the problem of freezing a semi-infinite region with finite surface conductance was programed in a digital computer through the finite difference method. A family of curves for the correction of the London-Seban solution was given in a dimensionless plot for different ratios of heat of fusion and specific heat effect; it was shown that the London-Seban solution when applied to the freezing of a mild steel slab under some particular conditions gave results in error by about 10 pct in the solidification rate. Although the Robertson-Schenck computer result has improved the London-Seban solution to a great extent, lack of generality and the tedious computing procedure have restricted its application. In this paper a "modified heat of fusion" which accounts for the effect of specific heat is defined, and is used instead of the actual heat of fusion in the London-Seban solution. An analytical expression of this modified heat of fusion in terms of the specific heat, surface temperature, and actual heat of fusion is derived by comparing the solutions of Stefan and London-Seban for the case of freezing of a semi-infinite region with constant surface temperature. It can also be extended to the case with finite surface conductance, and the results show good agreement with the Robertson-Schenck computer solution. The expression of the modified heat of fusion, the accuracy of the London-Seban solution, and the temperature distribution within the solid are presented graphically in dimensionless form. Numerical solution for the freezing of iron indicates that the ratio of the modified heat of fusion to the actual heat of fusion increases from 1.04 to 1.40 as the surface temperature decreases from 2700° to 1600°F.

Jan 1, 1969

By R. B. Sosman, J. C. Hostetter

We have shown in the preceding paper that practically all natural oxides of iron contain a determinable percentage of ferrous iron, and in many cases the percentage approaches that in magnetite itself. Some of these oxides are true homogeneous solid solutions. Others are not homogeneous, and can be separated magnetically into fractions. The nature and cause of this inhomogeneity in certain special cases form the subject of the present paper. Magnetic FRactionation of Oxides of Iron The magnetic fractionation of a sample of oxide can be conveniently carried out by powdering the material very fine, and exposing it at various distances from the poles of an electromagnet. The magnet that we used was specially designed1 to give a strong field together with a steep gradient outside of the poles. It is set in a frame, with the pole pieces directed downward. A glass plate can bc adjusted at various distances beneath the poles. If the fine iron oxide powder is placed just beneath the glass plate, successive portions of the powder are picked up by the magnetic attraction and are caught against the glass plate, the most magnetic portions being taken up at the greatest distance from the poles. Some natural oxides can thus be separated into several fractions of different magnetic susceptibilities. Among other natural iron oxides, we examined the powder obtained by crushing some crystals of hematite from Elba.2 We found that

Jan 1, 1918

By D. Krammer, E. S. Machlin

The effect of a brior high-temperature creep strain on the low-temperature ductility of commercially pure nickel has been evaluated. The low-temperature (-196°C) ductility decreases linearly with an increase in prior high-temperature (920°C) creep strain. The effect is experimentally correlated to the formation of inter crystalline cracks and voids during the prior high-temperature creep strain. The magnitude of the effect is also believed to be a function of the notch sensitivity of the material. SEVERAL mechanisms have been presented to explain the process of inter crystalline cracking in metals undergoing high-temperature creep. zenerl has suggested that grain boundary relaxation of shear stresses could build up high stresses at ob- stacles to grain boundary shear and thereby nucleate a crack. Chang and rant' have experimentally demonstrated that cracks do form at obstacles to grain boundary shear such as lines where three grains meet. The role of vacancies in the mechanism of high-temperature inter crystalline cracking has been explored by Machlt with the conclusion that the nu-cleation of voids by vacancy condensation is almost

Jan 1, 1960