Search Documents

By W. A. West

One who attempts to collect and classify equilibrium data from various iron-alloy systems is soon struck with the absence of any quantitative theory that can serve as a general background against which to compare and contrast results from different systems, at different temperatures, and with different concentrations. It is not necessary to wait for a perfect theory; investigation of divergences of theory from observation may prove of great value in acquiring understanding of the subject. For example, one has only to think of Raoult's law as applied to aqueous solutions. The equations developed by Zener1 represent an effort to provide such a quantitative theoretical background, and it is therefore desirable to subject this theory to such tests as can be applied. The present article is intended to be an application of available tests, and may thus be considered as a supplement to Zener's paper. It is assumed that this paper is available to the reader. The equations make it possible to calculate the effect on the equilibrium concentration of one alloying element due to the presence of one or more other elements. In particular. they are intended to give, for alloy steels, the carbon concentrations in alpha and gamma phases in equilibrium with each other, and in gamma in equilibrium with cementite. They may, however, be modified for use for carbon-free alloys. A summary is given later of the equations used in analyzing the data in this paper, and the symbols are there defined. About 125 papers have been examined for experimental data suitable for this investigation. An effort was made to look up all available reports of ternary systems including iron and carbon, as well as similar systems of higher order. Supplementary material was also obtained from a number of binary systems. A few noncarbon ternary systems were also found to which these methods could be applied. A comparatively small proportion oi the papers read provided usable material. In many systems the number of quantitative observations made in the iron-rich region is extremely small, and the smoothed curves to be found in most published phase diagrams are entirely useless for quantitative treatment. This opinion is confirmed by the authors of the series on Alloys of Iron Research, whose remarks show clearly that they have no illusions as to the accuracy of many diagrams that they present. A further difficulty arises from the fact that these equations apply only to rather low percentages of alloying elements. The result is that at the lowest concentrations, where the best agreement might be hoped for, the errors of observation become relatively very large. The experimental difficulties in measurements of this kind of equilibrium are, of course, an old story.

Jan 1, 1947

By S. C. Sun, A. M. Gaudin

This paper presents the results of a. study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresisl-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation _ 4µ(300)² Z= kx in which z is the zeta potential expressed in in volts, µ the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas. The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mixture of water, copper sulphate and xan-thate, we can calculate the zeta coefficient

Jan 1, 1947

By A. M. Gaudin, S. C. Sun

This paper presents the results of a. study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresisl-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation _ 4µ(300)² Z= kx in which z is the zeta potential expressed in in volts, µ the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas. The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mixture of water, copper sulphate and xan-thate, we can calculate the zeta coefficient

Jan 1, 1947

By A. E. Beasley, Ike McKinney

Scale is a broad term which includes many types of mineral deposits which have limited solubility in water. These mineral components precipitate when combinations of scale-forming cations and anions exceed their solubility. Scale deposits are tightly bound to each other and to the metal surfaces of a water system. Precipitates that do not readily adhere to each other or to metal surfaces are known as sludges. Sludges are easily removed from a system by flushing. For example, a sludge is formed in the internal treatment of boiler waters with orthophosphates where the calcium is purposely precipitated as hydroxyapatite. Calcium phosphate would have a tendency to adhere to the boiler tubes except for the addition of tannins or lignins. These sludge conditioners maintain the precipitated calcium phosphate as a sludge which can be readily removed by boiler blowdown.

Jan 3, 1973

By R. J. Stokes

S. Floreen (international Nickel Co.)— One fairly simple way to differentiate between em brittle me nt due to surface microcracks or due to a dislocation barrier effect might be to load a brittle rock salt crystal in tension to some stress just below the fracture stress and then immerse the loaded crystal in water. If a surface film is retarding plastic flow then one should observe some plastic deformation of the rock salt as

Jan 1, 1962

By David L. Holt, Walter A. Backofen, Anwar-ul Karirn

ANNEALING the binary alloy, Mg-0.5 wt pct Zr in a hydrogen atmosphere results in extensive precipitation of zirconium hydride. The morphology of these precipitates has already been investigated.lm3 Squires, Weiner, and phillips4 found, following creep testing of the hydrided alloy at 450" and 500°C, that hydride denuded zones formed along grain boundaries that were aligned approximately normal to the tensile axis. Zone formation was attributed to diffusional creep by magnesium transport down the prevailing stress gradients.4'5 Recently, electron microprobe analysis by Karim, Holt, and Backofen6 showed the zones indeed to be zirconium-free and furthermore it was shown that in compression, zones formed along boundaries approximately parallel to the stress axis. Thus it was confirmed that the zones are formed by diffusional creep. Typical zone-formation is shown in Fig. 1. Karim, Holt, and Backofen also measured the con- tribution to the total strain, from diffusional flow, slip creep, and grain boundary shear: results showed that diffusional strain tends to saturate with increasing imposed strain, while grain boundary shear eventually becomes the dominant deformation mode. It was suggested in explanation that the precipitate-denuded zones are soft and easily sheared, such deformation contributing to the grain boundary shear measurement. A point to be emphasized is that the Mg-0.5 Zr alloy was not superplastic for the index of strain rate sensitivity of flow stress, m = a log log 6 was only 0.25. It was recognized that diffusional creep in a poly crystalline aggregate must be accompanied by boundary shearing.' The suggestion was that the non Newtonian-viscous character of diffusional creep in the Mg-0.5 wt pct Zr alloy is due to resistance to sliding of boundaries lying approximately parallel to the tensile axis.= The work described in the present note should be seen against the above background for it represents initial efforts to observe in a similar way diffusional creep in a superplastic alloy. Previous work with the ternary-alloy Mg-6 Zn-0.5 Zr, pellet extruded, showed it to be superplastic however it does not contain resolvable precipitates to act as internal markers for diffusional creep. Also the fine grain size of the alloy (0.5 p) made conventional metallography rather difficult. Solubility relationships in the Mg-Zn-Zr system are not well known, however making reasonable guesses about the probable phase diagram of the ternary, Mg-Zn-Zr, various heat treatments were attempted to produce hydride precipitation. Finally a 16-hr anneal at 495' in hydrogen was found to pro-

Jan 1, 1970

By K. T. Aust

It is proposed that the intergranular corrosion of austenitic stainless steels is associated with the presence of continuous grain houndary paths of either second phase, or solute segregate resulting from solute-vacancy interactions. Experimental observations of structural changes and crrosion behavior of different types of austenitic stainless steel provide support for this poposal. On the basis of this model, it is shown that the intergranular -corrosion susceptibility of austenitic stainless steels in nitric-dic hromate solution may be substantially reduced either by suitable heat treatments or by impurity control. AUSTENITIC stainless steels, such as Type 304, generally have excellent corrosion resistant properties when properly solution heat-treated and used at temperatures where carbide precipitation is slow. However, several corrosion environments have been found which produce intergranular corrosion of solu-tion-treated stainless steels, that is, those steels with no detectable carbide precipitation.''2 Of the various corrosion environments, the most widely used test solution has been the boiling nitric-dichromate solution. In these acid solutions, stainless steels have been found to be susceptible to intergranular attack despite the addition of carbide-forming elements such as titanium or columbium, or despite lowering of the carbon content or use of high-temperature solution treatments. Studies of the electrochemical mechanism of corrosion attack have been made by several worke1s3'4 who found that oxidizing ions such as crt6 depolarize the cathodic reactions and consequently raise the open-circuit potential of stainless steel immersed in nitric acids. As a result of this, the anodic reaction is accelerated. The reason for the localization of anodic activity at the grain boundaries, and resulting intergranular corrosion, has not been conclusively determined. Several workers, e.g., Streicher,3 and Coriou et al.,4 have suggested that the strain energy associated with grain boundaries provides the driving force for the accelerated intergranular corrosion. This argument would predict that alloys of high purity would still be susceptible to intergranular attack. However, work by chaudron5 and by ArmijO,6 has shown that high-purity alloys are immune to attack, in disagreement with this argument. An alternative suggestion is that chemical concentration differences exist between grains and grain boundaries, that is, impurity segregation at boundaries, and that these chemical differences provide the driving force for localized attack. It is this impurity segregation which can lead to accelerated dissolution of grain boundaries when the alloy is exposed to a suitable corrodant. This mechanism would predict the immunity of high-purity alloys to inter-granular attack, which is in agreement with experi-mental observations. In the present paper, some recent studies on inter-granular corrosion of austenitic stainless steels which were conducted by coworkers and myself will be re-tibility A simple model will be described in which it is proposed that the intergranular corrosion of aus-tenitic stainless steel is associated with the presence of continuous grain boundary paths of either second phase or solute-segregated regions.* On the basis of this model, it is suggested that the intergranular corrosion rate can be markedly reduced by the formation of a discontinuous second phase at the grain boundaries if the discontinuous second phase incorporates the major part of the segregating solute, drained from the grain boundary region. Results are presented of corrosion tests and electron microscopic studies of different types of austenitic stainless steel after various heat treatments which provide experimental support for this model. Finally, a solute clustering mechanism, based on a solute-vacancy interaction, is shown to be consistent with the results obtained for inter-granular corrosion of solution-treated austenitic stainless steels. EXPERIMENTAL Corrosion tests using weight loss measurements were made on sheet specimens, which were lightly electropolished, washed, and immersed in boiling (115°C) 5 N HN03 containing 4 g crt+6 per liter added as potassium dichromate. Studies in which the inter-granular penetration depth was measured both by electrical resistance and metallographic methods have shown an empirical correlation between the rate of intergranular penetration and the weight loss per unit time for identically treated specimens of stainless steel." As a result, although all the corrosion data reported here are in terms of simple weight loss measurements, these data are considered to reflect primarily the rate of intergranular dissolution. Fig. 1 shows a typical result of intergranular attack of a solution-treated Type 304 stainless steel after 4 hr in a boiling nitric-dichromate solution. The wide grain boundary grooving at the surface, and the attack at incoherent twin boundaries, are evident; very little corrosion attack is seen at the coherent twin boundaries. INTERGRANULAR CORROSION MODEL

Jan 1, 1970

By A. L. Holley

The first session was held in the rooms of the American Philosophical Society, on Tuesday evening, February 26th. The President, Dr. T. Sterry Hunt, called the meeting to order, and after a few introductory remarks concerning the importance of theoretical and speculative science, which often involves principles of the highest economic value, and, more than all that, serves to enlarge our conceptions of the universe, and ennoble us, by the cultivation which it affords to our most exalted faculties, proceeded to discuss some points in the chemistry of the atmosphere. It is known that there is in the crust of the earth a great amount of oxidized carbon, not only in the shape of coal, but also in the graphite or plunlbago of the crystalline rocks, in the various bituminous shales or pyroschists, which are found in all succeeding rock-formations, and also in the forms of bitumen and petroleum. All the analogies of nature lead us to conclude that these various carbonaceous substances have had an organic origin, and have been generated by the deoxidation of carbonic acid, a process effected by the growing plant, and attended with the liberation of oxygen. He showed that the carbon of a layer of coal covering the whole earth's surface to the thickness of one meter, would, in its production from carbonic dioxide, liberate an amount of oxygen equal to that now present in our atmosphere. But bituminous coal contains also a large amount of hydrogen, derived from the deoxidation of water, which implies the liberation of a farther portion of oxygen. The amount from this latter source would equal, for the various coals and asphalts, from one-eighth to one-fourth, and, for the petroleums, onehalf of that set free in the deoxidation of the carbon which these hydrocarbonaceous bodies contain. From what we know of the composition of the stratified rocks, it is probable that they include an amount of deoxidized carbon and hydrogen many times greater than that contained in a layer of coal one meter in thickness, and, consequently, that the disengaged oxygen in past ages must have far exceeded that now present in our atmosphere. To this must be added

Jan 1, 1879

By F. W. Schaller

TETRAGONALITY is an important aspect of the models of transformation, strengthening, and tempering of ferrous martensite. When the c/a

Jan 1, 1963

By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

By Y. Nakahiro

The removal of heavy metal compounds from a synthesized waste cyanide solution is achievable by a precipitation-flotation method. However, the differential separation of constituting metals by this method was thought to be very difficult. The present author found that addition of ferrous salt to the synthesized waste cyanide solution of cadmium and copper can modify the separation characteristics of these metals. In this paper, the separation of cadmium from copper in the synthesized waste cyanide water by the precipitation-flotation method is discussed. This differential flotation uses ferrous salt as a precipitant and sodium oleate as a collector. Based on a series of fundamental flotation tests, actual differential flotation tests were made. The separation of cadmium from copper in the synthesized waste cyanide water was found to be satisfactory. This method can be effective for the removal of difficult-to- separate colloidal precipitates from liquids by the sedimentation method, provided the applicability of this method to the separation of the other metals is promising. This consists of the intensive studies which have been conducted at author&apos;s laboratory.

Jan 1, 1980

By P. Greenfield, P. A. Beck

The phase is a hard and extremely brittle material with a tetragonal crystal structure, containing 30 atoms per unit cell&apos; It occurs in many binary and ternary alloys of the transition elements. The existence of twelve a phases has been reported in binary alloys of metals from the group vanadium, chromium, molybdenum, and tungsten with metals from the group manganese, iron, cobalt, and nickel. It is a characteristic fact that the composition of the o- phases in the various binary systems is not the same. Rather, there is a gradual shift in composition, for instance in the series of chromium a phases, approximately as follows: CrMn,, FeCr, Cr3Co,. In recent years several ideas have been put forward to account for this variability of composition. SullyZ proposed that a was a type of electron compound, characterized by 1.7 electrons per atom in excess of the number required to fill the Pauling atomic orbitals. These excess electrons were supposed to just fill the first Brillouin zone of the u structure. However, later work indicated that the phase is ferromagnetic at low temperatures, so that a- is unlikely to be a full zone compound.~ Another proposal,* which is also based on the structure of the transition elements advanced by Pauling, and in fact leads to essentially the same a compositions as Sully&apos;s theory, suggests that the u phase is characterized by a constant number of electron vacancies per atom. The electron vacancy numbers N,. used were originally the same as those in the Pauling theory, but were later modified empirically vn order to bring about better agreement with data for the p phase in certain ternary systems. For alloys, N,, was calculated on the assumption of simple additivity from the electron vacancy numbers of the components, as follows: N,. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2 (Fe) + 1.71 (Co) + 1.6 (Ni). On this basis a reasonably constant value of N, = 3.4 was obtained for all of the binary u phases and a fairly constant value of N,, = 3.1 for the various p phases. More recently, Bloom and Granta pointed out that a similar correlation with the total number of 3d and 4s electrons per atom is also fairly well fulfilled and concluded that no reference need be made to the Pauling theory. This proposal does not lead to the same binary a compositions as the one described above, so that the relative merits of the two proposals may be determined on the basis of direct comparison with experimental composition data. The purpose of the present paper is to provide such a comparison. Since the experimental data for the composition ranges of several of the known u phases were rather incomplete, it was decided to carry out new experimental determinations for many of the binary systems. Experimental Procedure The alloys were prepared by induction melting in recrystallized alumina crucibles, either in vacuum or in helium atmospheres. Some aluminum was picked up from the crucibles in the alloys of high vanadium content, but this was minimized by keeping the alloys in the molten state for as short a time as possible. The maximum aluminum impurity was 0.13 wt pct by chemical analysis, in an alloy containing over 50 wt pct V. In general, the as-melted compositions agreed accurately with those obtained by chemical analysis. In the case of manganese, however, losses inevitably occurred; consequently all manganese alloys were analyzed. Specimens of all alloys were annealed at temperatures ranging from 1000" to 1300°C in an atmosphere of purified 92 pct helium and 8 pct hydrogen mixture. All manganese alloys were sealed in quartz tubes under vacuum before annealing. The specimens were held at temperature for between four and eight days before being quenched into cold water. Alloys were prepared for microscopic examination by mechanical polishing, usually followed by electrolytic etching. X-ray diffraction specimens were prepared by crushing the homogenized alloys, and by reanneal-ing the obtained powders in evacuated quartz tubes for a few hours at the temperature of the lump anneal. X-ray diffraction patterns were made with unfiltered chromium radiation, using an asymmetrical focusing camera of high dispersion. Using microscopic and X-ray techniques jointly, the accuracy

Jan 1, 1955

By R. A. Vandermeer, P. Gordon

The study of recrystallization in cold-worked metals is complicated by the impossibility of making direct three-dimensional optical measurements. Metallo-graphically, theinternal three-dimensional features of samples must be inferred from their intersections with the two-dimensional plane of polish. The inherent difficulties involved in this procedure have led— particularly during the last few years—to some instances of rather doubtful interpretations of experimental data in terms of nucleation and growth rates in recrystallization. In the present paper an analysis ; is given of the recrystallization characteristics in a polycrystalline alloy containing 0.008 wt pct copper in ZONE-refined aluminum *and an effort is madf to reemphasize the necessity in such studies for attention to the proper statistical relationships between one- two- and three-dimensional features of opaque samples. It is shown that, in common with several recently described cases for other types of transformations,1-5 recrystallization in this alloy can best be rationalized on the basis that all nucleation took place essentially at time zero—i.e., there is no significant time-dependent nucleation during annealing—and that the kinetics are controlled exclusively by the growth-rate parameters. This is true despite the fact that the number of

Jan 1, 1960

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:&apos; C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:&apos; C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By C. E. Sims, C. A. Zapffe

MANY hundreds of publications have appeared during the past 78 years that treat the subject of hydrogen in iron and steel,105 but conclusions regarding the functions of hydrogen in causing some important defects in steel are still unsatisfactory to many; and other hydrogen-caused phenomena yet remain to be identified with this gas. The most widely discussed of these defects is hydrogen embrittlement, but the conception, perhaps the popular one, that embrittlement is due to hydride formation does not conform to the known facts.104 The true identity of hydrogen embrittlement seems instead to lie in a mosaic nature of metal crystals, which is a concept not yet accepted by most metallurgists. A study of hydrogen embrittlement therefore provides new viewpoints in regard to the crystalline substructure of steel. A second widely discussed hydrogen-caused defect is the "flake" or "shatter crack." Although it is generally agreed that the presence of hydrogen is a prerequisite for their appearance, it is also realized that internal stress plays a decisive part. The relationship of hydrogen to internal stress has not been explained very clearly; nor is it always clear what the relationship is between a "flake" and a "snowflake," or between a "fish eye" and a "shatter crack." More importantly, the relationships among hydrogen embrittlement, hydrogen-caused fissures such as "flakes" and the ultramicroscopic structure of steel have scarcely been recognized. The present investigation attempts to provide an explanation for the embrittlement of steel by hydrogen by showing cause for accepting the "block" concept of metal crystals, and then to show how the numerous hydrogen-caused defects are interrelated in the light of this concept. EVIDENCE OF SUBSTRUCTURE IN METAL CRYSTALS It appears that the concept of a crystal as an aggregate of smaller multi-atom units must be accepted in some form if the behavior of metals is to be understood. The abundant literature on the evidence of an ultramicroscopic "mosaic" structure in metals and other crystalline substances suggests that the physicist has provided the metallurgist with an invaluable new insight. The exact picturization that any one physicist provides may be open to question, but the fact that there is some such fundamental substructure seems undeniable. The present work makes no pretense of comprehensively treating the imperfection structure theories. Nor will conclusions be drawn here regarding the exact nature of the substructure of crystals. However, the acceptance of some imperfection theory of fundamental attributes seems so necessary to an understanding of the behavior of hydrogen in steel that the following brief

Jan 1, 1941

By J. F. Shea, O. F. Tangel

Battelle Memorial Institute participated in a program for the General Services Administration aimed at developing a nickel-cobalt separation process that could be integrated in the Nicaro nickel plant. At the time the programwas being carried out, the Nicaro process was a straight-through operation, in which the ore was reduced and leached, after which the pregnant solution was boiled to produce a so-called "bulk precipitate" which contained virtually all of the nickel and cobalt which had been dissolved in the leaching step. The weight ratio of nickel to cobalt in Nicaro ore is approximately 15 to 20:l. The weight ratio of nickel to cobalt in the finished product had to be 100:l or higher to meet specifications. Because the Nicaro process embodied no nickel-cobalt separation step, the only way that a bulk precipitate of the specified nicke1:cobalt ratio could be produced was to so adjust roasting and leaching conditions that nickel would be selectively leached and most of the cobalt would be rejected with the tailings. The required selectivity, however, was achieved at the expense of nickel recovery, which was 5 or more per cent less than might have been obtained with the existing equipment, utilities, man power, etc., had selectivity been no object. The over-all purpose of the program was to develop a separation step that could be fitted into or onto the Nicaro facilities and which would permit the manufacture of a product that would meet the desired specifications and still permit the recovery of a maximum amount of nickel. Battelle suggested that this might be accomplished by reprocessing off-specification bulk precipitate and specifically suggested the process based on ammonium sulphate leaching followed by hydrogen reduction of the leach solution according to techniques developed commercially by Sherritt Gordon Mines Limited. Such a process would not only satisfy the objectives of the research but would present two additional advantages. (1) It would produce a separate cobalt product which could be further processed into metal, alloys, oxides, or salts. (2) It would yield nickel in metallic form which might be more generally marketable and command a slightly higher price per unit of nickel than the Nicaro oxide product. DESCRIPTION OF THE PROCESS Figure 1 is a flowsheet of the process. The essential features are: (1) Extraction of about 97 per cent of the nickel and about 85 per cent of the cobalt from bulk precipitate by a principal leach with ainmonium sulphate solution (Step A). Extraction of virtually all of

Jan 1, 1961

By N. A. Gokcen

The construction and operation of a simple and accurate vacuum-fusion apparatus are described in detail. Absolute accuracy of the oxygen analysis has been determined by the reduction of oxides weighed to 20.01 mg. The Bureau of Standards steel samples have been analyzed repeatedly, and their inadequacy for the acceptable range of oxygen is presented. The limits of interference of manganese, aluminum, and titanium, and the effects of tin and water-cooling of the furnace tube have been investigated in detail. ANALYSIS by the vacuum-fusion method consists of melting a sample in a degassed graphite crucible under high vacuum and extracting oxygen as carbon monoxide, and nitrogen and hydrogen as gaseous elements. The resulting gas mixture is analyzed for its constituents, from which oxygen, nitrogen, and frequently hydrogen may be determined within 1/2 hr or less. The history and summary of methods1-4 and extensive reviews of literature&apos;.&apos; for the determination of gases in metals have been published in detail. The foundation of the modern vacuum-fusion method of analysis was laid by Jordan and Eckman,11 and Oberhoffer and his associates.1, 10 Diergarten,11, 12 Meyer,13 Thanheiser et al.,14, 15 Ericson and Benedicks,16 Ziegler,17, 18 Sloman,16-23 Thompson et al.,24 and later many others contributed to the improvement, accuracy, and limitations of the method. In some investigations, however, the limitations of the procedure and the errors involved in the analysis require further critical examination and evaluation. In many apparatuses, lunnecessarily complicated and cumbersome features and elaborate precautionary measures do not have conclusive advantages. The purpose of this invest:igation was, therefore, a) to construct a very simple and accurate apparatus, b) to determine the absolute accuracy of results, c) to establish the limits of interference of manganese. aluminum, and titanium, d) to reexamine critically the reduction and recovery of oxygen from oxide powders of various sizes, and e) to evaluate critically the eight steels of the Bureau of Standards."&apos; Apparatus The apparatus used in this investigation is shown in Fig. 1. It has been used for over three years, during which several modifications were made. A brief description of the apparatus is as follows. The transparent silica or Vycor tube, E, is joined to the Pyrex head, B, by mean of a face to face ground joint sealed with mercury. A similarly sealed ball and socket joint would also have been satisfactory. A standard tapered ground joint, successfully used by some investigators, was tried, but in the absence of grease or vacuum cement it was very difficult to disassemble the joint. The graphite crucible, G, 15/16 or l 1/8 in. OD, 2 1/2 or 3 in. high, 1/10 in. wall, shown enlarged in Fig. 3a, is made from the rods containing less than 0.08 pet ash. Two baffles, overlapping sufficiently to prevent spattering, are inserted in two opposite slots cut on a band saw. Two small holes in the baffles permit the temperature measurement of the melt. A second type of crucible, Fig. 2, G, shown enlarged in Fig. 3b, is also satisfactory, though not as convenient as the crucible shown in Fig. 3a. Somewhat similar but more elaborate crucibles with baffles were first tried by Ericson and Benedicks,&apos;" but were abandoned in favor of a crucible with a stopper and a peripheral graphite powder filter. Various versions of their crucible with a stopper have later been used by other analysts, 10-27, 27-30 The crucible is packed directly in E, Figs. 1 and 2, with —35 + 48 graphite powder for shielding and insulation. A minimum layer of 7 mm of powder is necessary for keeping E cool and minimizing the blank. The first use of graphite powder was made by Sloman,10-23 Who found that —200 mesh was the most satisfactory. The author tried various size powders from +20 to —100 mesh and found that a) particles of 28 mesh or larger were not sufficiently insulating and were heated by the induction current, b) the powder finer than 60 mesh packed too much and did not readily permit the escape of gases even when the crucible was heated very slowly; hence, the powder was occasionally blown out of the side in the crucible and in the mercury pump. The optimum size powder is, therefore, 35 to 48 mesh size or 0.4 mm in average diameter. The furnace is designed to eliminate excessive amounts of

Jan 1, 1959

By J. E. Berg

THE geology of the Coeur d&apos;Alene mining district is so familiar to every one interested in mining that I will only note as an introduction that the main producers are mines whose orebodies lie in the Revett or Burke quartzites ; that the known orebodies in the eastern part of the district all lie north of the Osburn fault; that the Prichard formation is quite generally looked upon as being unfavorable for lead deposits ; that the monzonite intrusive mass extending north from Gem to Sunset Peak, and over into Cedar Creek divide, is considered to have been the prime agent in the crea-tion of our orebodies, and that diabase dikes are a quite common feature at most of the properties with which I am familiar. Some of the exceptions to these statements may be mentioned. The Interstate-Callahan mine is considered the exception disproving the alleged relation between large ore-deposits and the Prichard formation, but this property was primarily a zinc producer, with lead secondary, though of sufficient tonnage to be a valuable product. A second interesting occurrence in the Prichard worth calling to your attention is the Jack Waite property, on Tributary Creek, north of Murray. This vein lies at a low horizon in the Prichard forma-tion, and the ore differs essentially from others in the same horizon elsewhere in that it is a clean, medium to coarsely crystalline, lead ore carrying very little zinc, about one ounce silver to ten units lead, and is accom-panied by a clean quartz gangue or vein filling. I believe that quartz was the primary mineral in the fissure, and that the lead ore was deposited in the vein as a replacement of the quartz.

Jan 7, 1927

[ARTICLE I. NAME AND OBJECT Section 1. This Society shall be known as the Society of Petroleum Engineers of the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. Section 2. The object of the Society of Petroleum Engineers shall be to furnish a medium of cooperation among those interested in the petroleum-natural gas industry an to promote the advancement of this branch of mineral technology through meetings to stimulate the preparation, reading, discussion and circulation of papers connected therewith. ARTICLE II. MEMBERS Section 1. Any person who is a member of AIME may become a member of this Society by the specified process. Section 2. Local organizations may be formed by the Society of Petroleum Engineers as subsidiary units, the membership of which shall be subject to and in accordance with the by-laws of the Institute.]

Jan 1, 1961