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By D. Cox, M. J. Duggin, L. Zwell

The carbides of approximate composition and Mn have been studied using X-ray diffraction techniques. Those carbides of the type (Fe,Aln)zC ave isostructural with cementite. The cell pararmeters a and c have minimum values at approximately 10 at. pd substitution of manganese for iron; no satisfactory explanation has yet been found for this phenomenon. The carbide fFeMn4)C has a monoclinic unit cell whose dimensions are close to those of ,11,15Cz A neu-troip-dij~ractiot~ study of (F'eAlrz4)C~ reveals that, like MnsCZ, it is isostructural with Pd5Bz. The iron and manganese atoms occupy the palladium atom sites, while the carbon atoms were found to have the same atomic coordinates as the hovon atoms. A neutrorr-diffraction study of indicates that the carbon-atom positions are very close to those occupied in (Fez.,ll/lr~,.3)C. In both carbides studied, tlre iron and manganese atomzs were found to be essentially randomly distributed, although, in the case of (Fe,.811fn1.2)C, it is possible that there may be a slight preference of manganese atoms for- the general (d) positions and a corresponding slight preference of iron atoms for the special (c) positions. It has been found that a complete range of solid solution exists between Fe3C and Mn3C at 1050°C,I although Mn3C becomes unstable when the temperature is reduced to 95O0C,' and can only be retained by rapid quenching. It is also known that a complete range of solid solution exists from Fe5Cz to M~SC~,~ although the stability range of carbides of the type (Fe,Mn)sCz as a function of the relative proportions of iron and manganese is not known. X-ray examinations of Oh-man's carbide3 and Spiegeleisenkristall,~ which have the approximate compositions (Fe3.67Mnl.33)C2 and (Fe3-,Mn,)C, where x lies between 0.4 and 1, respectively, have been made. The following carbides have also been studied: ] The lattice parameters determined during these investigations are listed in Table I. It is seen that carbides of the type (Fe,Mn)sCz have a monoclinic unit cell while carbides of the type (Fe,Mn)3C have an orthorhombic unit cell. It is evident that the variation of lattice parameters with manganese content is not linear for carbides of the type (Fe,Mn)3C. The coordinates of the atoms in (Fe2.7Mno.3)C have recently been determined by single-crystal analysis., The fractional atomic coordinates have been shown by Fasiska and jeffrey to be in good agreement withj those deduced from an earlier analysis of Fe3C by Lipson and etch.' However, it was impossible to determine whether iron and manganese atoms occupied ordered positions because of the small difference between the atomic scattering factors of iron and manganese. The atomic positions in Mn5Cz (Refs. 8 and 9) and Fe5C2 (Refs. 7 and 8) have been obtained only by comparisons made with the isostructural compounds P~SB~.' Since X-ray diffraction techniques were used in these investigations, accurate positioning of the carbon atoms, which have a low atomic scattering factor, was difficult. No attempt has been made to determine the atomic positions in the other carbides previously studied. It was felt that an investigation of the lattice parameters of a number of intermediate carbides of the types (Fe,Mn)sCZ and (Fe,Mn)& would be of interest. It seemed likely that a neutron-diffract ion study of such carbides would indicate whether ordering occurred between the iron and manganese atoms because of the large difference between the neutron-scattering cross sections of iron and manganese. It also seemed probable that such an investigation would provide a determination of the atomic coordinates of the carbon atoms. I) EXPERIMENTAL DETAILS Specimens, each weighing approximately 20 g, were carefully prepared according to the following proportions: The components were 500-mesh powders of 99.995 pct purity iron and spectroscopically pure carbon and a 200-mesh powder of 99.995 pct purity manganese. The component powders were intimately mixed by prolonged shaking, then each specimen was inserted into a spot-welded cylindrical container of tantalum foil, whose end was closed but not sealed. Each specimen in its envelope was then sintered at 1050° C for 24 hr in a thin-walled evacuated quartz capsule, such a time having been previously found sufficient for equilibrium to be attained.' Each specimen was then quenched in order to attempt to retain the high-temperature phase, as the literature indicates that transformations may occur on cooling. Debye-Scherrer X-ray photographs were taken of each specimen using a 114.6-mm-diam camera, Fig. 1, patterns 2 to 6. The exposure time was 6 hr using filtered iron radiation at a tube voltage of 40 kv and a tube current of 12 ma.

Jan 1, 1967

By Sidney Diamond, Charles Wert

The anelastic behavior of Ni-C alloys of nominal 0.5 wt pct C has been determined over a wide temperature range. The most prominent damping effect, that due to the presence of C-C pairs, was measured both above and below the Curie temperature. The effect on diffusion of the C-C pairs by magnetic spin ordering is deduced to be very small. The diffusion coefficient for C-C pairs in nickel is given by the expression ThE solid-state diffusion of both interstitial and sub-stitutional solutes in ferromagnetic solvents has been the subject of a number of investigations. Measurements of the self-diffusion of iron,"' the diffusion of nickel1,4 gold,"1 and cobalt4 into iron, the diffusion of vanadium in an Fe-V alloy,' and the diffusion of cobalt and nickel in Co-Ni alloys9 show an unusual behavior. In both the ferromagnetic and paramagnetic regions, far removed from the Curie temperature, the diffusion coefficient, D, obeys an Arrhenius relation. However, in the ferromagnetic region D is markedly lower than would be expected from an extrapolation of D from the paramagnetic region; this results in an increase in the activation energy in the ferromagnetic region. The cause of this effect for self- and substitutional diffusion is uncertain. Since substitutional diffusion is presumed to proceed by the vacancy mechanism, it has been variously suggested that the increase in activation energy below the Curie temperature is due to one of the following causes: 1) an increase in the energy of formation of a vacancy because of local demagnetization around the vacancy,2,3 2) a decrease in vacancy mobility in the ferromagnetic state,' or 3) an effect on the entropy of motion of a vacancy in the ferromagnetic state.5 Quite another explanation for the observed effect has been proposed by Borg.7 The diffusion coefficient is a function of the elastic constants of a metal. Since the temperature dependence of the elastic constants often changes at the Curie temperature, the temperature dependence of D might be expected to undergo a universal change in the vicinity of the Curie temperature. The magnitude of the change in D would, of course, depend on the magnitude of the change in the elastic constants. One might attempt to differentiate between vacancy effects and elastic effects by making measurements on interstitial alloys, in which vacancy effects play no role. Some measurements of this type have been made; this paper reports additional observations. Measurements of the diffusion of carbon in a Fe by a tracer technique8 and of the diffusion of carbon in a Co and in Co-Fe alloys by a decarburization method9 reveal a small effect, if any, on D of the magnetic change at the Curie temperature. If the effect of spin ordering is only to alter the parameters controlling formation or mobility of a vacancy, interstitial diffusion should indeed remain unchanged through the magnetic transition, as these measurements imply.

Jan 1, 1968

By D. J. McAdam, G. W. Geil, R. W. Mebs

AS shown in previous papers by the authors 9-l7† the resistance of a metal to fracture, like its resistance to plastic deformation, is a function of all three principal stresses.‡ A technical cohesion limit is the technically determined resistance to fracture under a specific stress system. The technical cohesive strength thus comprises an infinite number of technical cohesion limits corresponding to the infinite number of possible combinations of the principal stresses. The technical cohesive strength, therefore, may be represented by a surface in a diagram with the three principal stresses as coordinates. As shown in previous papers, 9-I8 the technical cohesive strength increases with plastic deformation, with decrease in temperature, and with increase in the strain rate. The technical cohesion limit, therefore, is affected by the same factors that affect the flow stress, § namely, the stress system, plastic deformation, temperature, and the strain rate. More- over, the influence of each of these factors on the technical cohesion limit has been shown to be qualitatively similar to the influence of the same factor on the flow stress.9-18 Advance of knowledge about the conditions determining fracture, of metals has been retarded by the reluctance of some investigators to abandon preconceived ideas about how metals "should" behave. The incorrect idea is still prevalent that the conditions determining resistance to fracture are very different from those determining the flow stress. Attempts are still being made to express resistance to fracture in terms of a single parameter, such as a limiting value of the greatest principal stress, the maximum shearing stress, or the volume stress (one-third the algebraic sum of the three principal stresses). In these attempts, a sharp distinction is sometimes made between a ductile or "plastic fracture " and a "brittle fracture." In making this distinction, however, the meaning attached to the term "brittle fracture" sometimes is not made clear. The term could mean fracture after very little plastic deformation or it could be used to designate the type of fracture. An ordinary fracture of a ductile metal at room temperature starts as a cleavage, generally transverse to the direction of the greatest principal stress, but eventually changes to a shearing fracture. In some conditions, however, the metal fractures entirely by cleavage, with no evidence of plastic deformation during the fracture; the surface of such a fracture may have a

Jan 1, 1947

By C. Goldberg, R. H. Wynne

WHEN using an optical goniometer to determine crystal orientation' it is advantageous to use a preferential etchant so that the etch pits have plane faces which are parallel to crystallographic planes, all of which are of the same "form." "Westinghouse Silver Etch" (WAg), a preferential etch for germanium, is made up as follows: 40 ml of 49.7 pct hydrofluoric acid, 20 ml of 70.7 pct nitric acid, and 40 ml of distilled water containing 2.0 g of silver nitrate. Examination of metallographs of WAg etched surfaces (Fig. 1, for example) indicates that, regardless of crystal orientation, the faces of the etch pits are (111) surfaces. Optical goniometer examination of these WAg etched surfaces also indicates that the faces of the etch pits are (111) surfaces, i.e., all bright reflections are from (111) planes. When using an optical goniometer of the type described by Barrett,' not only (111) reflections from a WAg etched germanium surface but also other reflections of lower intensity will be observed. These latter reflections can cause confusion. We have used an optical goniometer made from a war surplus astrocompass and a galvanometer lamp. The reflections are observed by using the goniometer in a darkened room and letting the reflected light be in- cident upon a piece of white paper. The resulting decrease of goniometer sensitivity enables (111) reflections only to be observed. This in turn permits the crystal orientation to be determined in a matter of minutes, since only two measurements are necessary. The authors wish to acknowledge the help received from R. E. Davis who assisted in making the metallographs and aided the authors in the interpretation of the metallographs.

Jan 1, 1954

By F. S. Peabody

ANYTHING that may be said about "too much coal" must seem rather incongruous just at this time when two-thirds of the mines in the United States have been idle for nearly four months and a temporary coal shortage looms as more and more of a possibility. It is the purpose of this article, however, to deal primarily with the fundamental ills of the bituminous-coal industry, which, when summed up, can be expressed in one word-overdevelopment. During recent years the bituminous-coal industry in the United States has been seldom, almost never, in a state of normal business health with production run-ning evenly, prices steady and the market absorbing the output from week to week. There has been either a condition of feverish activity or apathetic sluggish-ness. We have had, for example, the intense strain on production during the war years with heatless days and lightless nights, followed by the slump late in 1918 which lasted through the greater part of 1919 when coal was a drug on the market. Then came the panicky demand of 1920. Competitive buying forced prices up to the highest levels in history. This demand in turn fell off suddenly in November, 1920, and the market remained apparently paralyzed all through 1921. During the latter year, lack of buying forced intermit-tent suspension of mining in all fields and prices averaged less than actual cost of production.

Jan 8, 1922

By R. E. Miner, J. K. Jackson, D. F. Gibbons

Internal-friction measurements were made during isothermal aging treatments of 18 pct Ni maraging-steel wires between 420° and 612°C. A sharp initial drop in the internal-friction level was interpreted in terms of a rapid dislocation recovery reaction. The rate of the recovery was found to be independent of temperature. Truncation of the recovery reaction was apparent in those systems that exhibited the rapid age-hardening characteristics of the maraging steels. It is proposed that this initial hardening response is the result of a low activation energy preprecipitation reaction involving molybdenum. A gradual rise in the internal-friction level at longer aging times was associated with the precipitation of a molybdenum-containing precipitate. CONSIDERABLE research effort has recently been devoted to the mechanisms responsible for the high strength and toughness of 18 pct Ni maraging steels. These bcc martensitic alloys are found to harden during aging at temperatures between 400° and 600°C. The aging response is very rapid with more than half the total hardness increase occurring within the first few minutes of aging, Fig. 1. Precipitate particles have been observed in the later stages of aging by a number of investigators.'-' While the identity of the precipitates remains the subject of some controversy, one or more of the intermetallic compounds, Ni3Mo, Ni3Ti, and Fe2Mo, are almost certainly involved. Heterogeneous nucleation of precipitates at dislocations has been noted8 and cobalt is believed to enhance the formation of fine, homogeneously distributed particles by lowering the solubility of the alloying elements in the martensitic matrix.3,7 Transmission electron microscopy studies of the initial hardening behavior have not been fruitful. Strengthening mechanisms based on atomic ordering have not been generally supported by X-ray and neutron-diffraction experiments.9 In the present investigation, the aging reaction was studied using isothermal-aging internal-friction measurements. The marked sensitivity of internal friction to short-range diffusion and precipitation processes has provided a convenient tool for the elucidation of the strengthening mechanisms operative in the maraging steels. EXPERIMENTAL PROCEDURE An upright torsion pendulum was used to measure the internal friction of several maraging steels during isothermal aging. The pendulum was placed in an atmosphere of helium at a pressure slightly less than atmospheric. To permit measurement of internal friction during the first minutes of aging, the specimens were rapidly heated by passing a current through them in a manner similar to that described by Ang and Wert.10 Thermal gradients in the specimen were largely eliminated by using specially designed specimen grips11 which produced temperature variations of less than 1 pct over 90 pct of the specimen length and less than 3 pct over the entire length at aging temperatures up to 620°C. A proportioning strip-chart program controller was employed to maintain constant specimen temperature during treatments of up to 36 hr duration. A number of vacuum-melted laboratory heats having compositions near that of a typical commercial 18Ni-7Co-5Mo-0.4Ti alloy were investigated. The amount of cobalt was varied from 0 to 7 wt pct in five of the heats. Either molybdenum or titanium was omitted in the remaining two heats. The alloy desig-

Jan 1, 1967

How often have you faced the adjustable speed drive dilemma: Of all the medium horsepower drive variations around, which one is most cost-effective? Regardless of the industry-from mineral processing to power generation- there is always one optimum drive which will outperform the rest. Philadelphia Gear Corp. recently asked its applications engineers to identify the most typical questions they receive regarding adjustable speed drives. Over a wide spectrum of applications-such as drives for conveyors, crushers, fans, blowers, mills, pumps, and compressors- the following 20 questions surfaced most often. The questions, and our answers, may be helpful when evaluating your next medium hp adjustable speed drive application.

Jan 11, 1978

By J. D. Wood, J. T. Smith

ALLOYS with a dispersed second phase in a metallic matrix are generally much stronger than the matrix itself. Plastic deformation in dispersion-strengthened alloys is usually confined to the matrix phase when recovery processes are active, while in the absence of recovery both phases may yield.' The alloy system studied in the present research was WC-12 wt pct Co and consisted of noncoherent WC particles dispersed in the cobalt matrix. Some particle-to-particle contact existed but not enough to produce a continuous WC skeleton. The microstruc-ture of the WC particles was characterized by very straight edges, forming a trapezoidal shape in any plane of polish. Previous investigations with WC-Co alloys at room temperature have shown that fracture of the WC particles occurs in transverse rupture testing.' Room-temperature slip was reported for WC particles after indentation for hardness measurements.3 Elevated-temperature deformation of WC particles in a WC-12 pct Co alloy was suggested by recent electron microscope studies of specimens deformed at 900' to 1000°C.4 In highly deformed alloys, the WC edges were serrated in contrast to the usual straight or smooth appearance. WC-12 pct Co and WC-15 pct Co alloys have been previously studied under elevated-temperature com-pressive-creep conditions by the present authors. Electron microscope studies of two-stage replicas from deformed specimens showed no evidence of slip or fracture of the WC particles. These specimens were brought to temperature and allowed to equilibrate prior to the application of the creep load. It was believed that the load-application rate, a crosshead speed of 0.005 in. per min on an Instron universal testing machine, was sufficiently low that recovery within the cobalt matrix was sufficient to limit the deformation to this matrix. A series of experiments was performed to evaluate the influence of loading rate on the deformation of WC-Co alloys. A WC-12 pct Co alloy was selected for these determinations. The average WC particle size was 4.45 p with an average linear separation between particles of 0.59 p. The selected temperature was 800°C and was monitored with a Chromel-Alumel thermocouple attached to the specimen. Testing was conducted in an argon-atmosphere chamber to prevent oxidation of the WC-Co specimens. This chamber was mounted on an Instron universal testing machine equipped to apply the load at a fixed rate. Each specimen was loaded to 110,000 psi compression stress at 0.05 and 0.5 in. per min. The loading rate was monitored prior to insertion of the test chamber and was found to be almost precisely the nominal rate selected. The specimens were raised to temperature and held to equilibrate with the surroundings, and then the load was applied and held for 4 hr to duplicate the exposure time utilized for the creep specimens. The time to reach full load at a crosshead speed of 0.005 in. per min was some 500 sec and was reduced to 50 and 5 sec as the loading rate was increased to 0.05 and 0.5 in, per min, respectively. The model developed by Ansell,' when recovery processes do not occur, considers that fracture or deformation of the dispersed particles is necessary to relieve back stresses on dislocation sources and allow dislocations piled up against particles to sweep out in the matrix to cause plastic deformation; he further states that, even at elevated temperatures, the dispersed-particle deformation is necessary for yielding in the absence of recovery. For the case of straight dislocation segments piled up against a straight barrier, such as the straight-sided WC particles, the shear stress, 7 exerted on a particle is: where h is the spacing between particles (0.59 p), a is the applied stress (110,000 psi), p, is the shear modulus of the matrix (6.7 X lo6 psi at 80O°C), and b is the Burgers vector of the matrix dislocation. From Eq. [I], the shear stress, 7, exerted on the WC particles when no recovery occurs is of the order of 6 X lo6 psi at 800°C. The limiting stress, F, that will

Jan 1, 1969

By A. M. Gavdin, F. W. Bowdish

Mineral dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,? its magnetic remanence,³ the turbidity of its suspension," and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid—both internal and external—the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample.2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. Apparatus In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. I and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1947

By A. M. Gavdin, F. W. Bowdish

Mineral dressing is an industrial art concerned with the treatment and separation of solids suspended in fluids. Knowledge and evaluation of the area of solid-fluid interface is important in all cases except those involving only large pieces of solid. In fact, many problems relating to comminution, to flotation, to thickening and classification, could be dealt with more rationally if the interfacial area were known. A number of methods have been proposed for the measurement of the surface of certain finely divided solids. Among them are methods using rate of dissolution of the solid,? its magnetic remanence,³ the turbidity of its suspension," and the character of the size distribution of the material.9 The first two are limited to one mineralogical species per sample; the third has certain optical limitations, especially for mineral mixtures, and the fourth is based on an extrapolation of uncertain validity. The need of a better and more general method of surface determination has long been felt, therefore. The method of P. H. Emmett,4 based upon the low-temperature adsorption of vapors, appears to fulfill this need. This method consists in determining the amount of nitrogen that is adsorbed by a given sample of solid at the temperature of boiling nitrogen. The more surface there is on the solid—both internal and external—the more nitrogen is abstracted. In actual operation, the method is somewhat less simple than has been stated so far, in that the nitrogen is adsorbed in an incomplete layer, the completeness and thickness of the layer being related to the pressure of the nitrogen in contact with the sample.2 This circumstance makes it necessary to determine the nitrogen adsorption for three or more values of the nitrogen pressure. Apparatus In the Richards Mineral Dressing Laboratories an Emmett apparatus has been built and tested (Figs. I and 2). A mechanical vacuum pump B and a mercury diffusion pump A work in series to give a high vacuum. The sample, placed in bulb D, can be evacuated by this pump train by suitable operation of the stopcocks in the glass tubing that connects the various parts of the apparatus. C is a McLeod gauge, used to ascertain the order of magnitude of the vacuum obtained, and not for accurate pressure measurements. Pressure measurements are made in the mercury manometer F and gas-volume measurements in the gas burette E. Gases are stored in flasks L (nitrogen) and K (helium), arranged so that definite quantities of these gases can be introduced into

Jan 1, 1947

By N. K. Chen, R. Maddin

Columbium single crystals were deformed in tension and compression. Reorientation by X-rays and stereographic projections of slip traces indicate that plane of slip may be considered as (110). The plastic behavior is shown to be quite similar to the deformation of molybdenum single crystals. STUDIES on the crystallography of the deformation process in body-centered cubic metals have been renewed recently with investigations of iron single crystals1-" and molybdenum single crystals.4 It is now apparent that too many exceptions to the rationalization based upon the ratio of absolute testing temperature to absolute melting point by Andrade5 exist to permit more serious discussion of this type of analysis. The considerations of resolved shear stress utilizing only planes of the type {ll0}, {112), and {123)³,6 permit analysis of the deformation only on the basis of those three types of planes. The suggestions made by Elam7 and by Greninger8 in which the slip process is envisioned as a composite slip on two nonparallel {110) planes can be illustrated schematically in Fig. 1. It may be seen that an unresolved trace on any plane containing a <111> direction may be accomplished by varying the number of atoms participating in the composite process. By further varying the number of atoms in each plane but keeping the ratio of participating atoms constant, jogs could be obtained in the traces and hence wavy slip lines could be produced. Vogel and Brick&apos; studied the behavior of a iron single crystals in which they suggest that the plane of glide is "non-crystallographic" and may be predicted from the intersection between the great circle joining the slip direction and specimen axis with the great circle whose zone axis is the slip direction. In a more recent investigation on iron single crystals, Steijn and Brick" suggest that the slip mechanism may be considered as made up of a type of composite slip occurring on {110} and {112} planes. Evidence for a possible composite nature of the slip process has been presented for the case of molybdenum in the form of analysis of asterism and specimen axis rotation." Definite proof of a composite slip process must, however, await good electron microscopic resolution of the individual traces making up the unresolved optical trace used in determining the acting slip plane. The present investigation was undertaken to study the behavior of columbium single crystals not only in tension but also in compression since the specimen axis migration should indicate the plane or planes of glide in the same manner that the specimen axis migration in tension indicates the direction of glide. The orientations of eleven crystals investigated are shown in Fig. 2. Specific orientations are missing (those in the vicinity of [Ill] and [001] and consequently the effect of orientation on the crystallography of deformation could not be considered. Experimental Procedure The 1/8 in. rods (7 in. long) were subjected to an axial tension in vacuo while at temperatures in the vicinity of 2000°C for 2 to 4 hr. This treatment resulted in large cylindrical grains (about ½ in. long) occupying the entire cross section. A number of these rods were used for the tension studies by observing the behavior of the individual grains. For the compression studies, single crystals approximately % in. long by 1/8 in. in diameter were cut from the rods; the ends were ground parallel. All specimens were polished electrolytically in a solution of 15 cc HF(48 pct) and 85 cc H2SO4 (concentrated) using a platinum cathode, a current density of 0.04 amp per sq cm and a temperature between 25" and 60°C.10 Orientations were obtained using a Laue back-reflection method (3 cm film to specimen distance) with a ½ mm collimator 9 cm long. For the compression specimens, a reference mark was scratched on one of the compression sur-

Jan 1, 1954

By Frank Firmstone

IN the early decades of the past century the method of starting iron blast-furnaces by "scaffolding-down" seems to have been in universal use for coke-furnaces and, at least in this country, for charcoal-furnaces also. It was likewise used at some of the early anthracite-furnaces, as is stated in the important "Reminiscences" printed by the late Samuel Thomas. I It had been generally superseded in Great Britain as early as 1850, by some variations of the plan now used, and was rarely used when Percy wrote.&apos; On the Continent it was still followed in the 60&apos;s,3 and was elaborately described by Valerius in 1852. I have never read any statement as to when and by whom &apos;4 scaffolding" was first dispensed with, but the following extracts from journals of my father seem to fix an authentic date for an instance in this country:

Mar 1, 1907

By D. A. Rice, M. C. Fuerstenau

Flotation data indicate that sulfonate and amine adsorb physically on manganese oxide; oleate also adsorbs physically if the zero point of charge is sufficiently high. Chemisorption of oleate occurs on pyrolusite between pH 8 and 9, and possible mechan- isms of collector adsorption involving metal ion hydrolysis are discussed. The flotation characteristics of most metal oxides1-15 have been examined with standard collectors such as fatty acids and sulfonates. From these studies it would appear as though electrical phenomena are important when shorte r-chained collectors are involved. For example, Iwasaki, Cooke, and Choi9 have shown that dodecyl amine and dodecyl sulfate float iron oxide above and below the zero point of charge, respectively. In another system, D.W. Fuerstenau and Modi10 have shown that dodecyl sulfate, dodecyl

Jan 1, 1969

By Yingchang Tsenshan Wang

UUIN L&SS 1» Paqb I. Introduction........................................................658 1. Subject and Scope...............................................658 2. Acknowledgments...............................................659 3. Review of Previous Work........................................659 Field Data...................................................659 Experiment.a1 Data............................................662 4. Plan of Present Investigation.....................................662 Method of General Procedure...................................663 I1. Experimental Work..................................................663 A. The Solution of Sphalerite..............................:........663 1. The Solvent Effect of Iron Sulphates upon Sphalerite...........663 2. The Solubility of Sphalerite in Salt Solutions of Silver, Copper and Lead...............................................668 B. Formation of Zinc Carbonates....................................674 3. The Reactions of Carbonates and Bicarbonates With Solutions of Zinc Salts............................................674 4. The Reaction of Zinc.Sulphate Solution With Limestones.......684 C. Peculiar Conditions Affectitig the Formation of Zinc Silicate (calamine) and Zinc Carbonate (smithsonite)..........................686 5a. The Effect of Carbon Dioxide Upon the Basic Silicate and the Carbonates of Zinc in Water, and Its Bearing Upon the Conditions of Theii Precipitation..............................686 5b. The Reactions of Solutions of Soluble Silicate With calamine and Smithsonite in Solution in Presence of Carbon Dioxide..689 6. The Reactions of a Mixture of Hydroxide and Silicate of Sodium with a Dilute Solution of Zinc Sulphate...................691 D. High-Temperature Methods.....................................692 7a. The Influence of Temperature on the Formation of Calamine..692 7b. Possible Effect of Heat on Calamine and Srnithsonite.........697 E. Summary of the Experimental Work..............................698 III. Petrographic Work....................................................700 1. The Occurrence of Sphalerite in Limestones or in Cherts............701 Summary of the Blende in Limestones and in Cherts.............7432 2. The Partially Altered Sphalerite and the Oxidation Products........702 a. Smithsonite with Blende....................................702 b. Calamine with Blende......................................703 c. Smithsonite and Calamine..................................703 d. Summary on the Partially Altered Sphalerite and Its Oxidation Products..............................................704 IV. Concl~~siom ........................................................-705 V. Microphotographs and Photographs with Their Explanations.............705

Jan 1, 1916

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890

Jan 1, 1923

By G. S. Ansell, J. Weertman

The creep behavior of an aluminum alloy hardened with a finely dispersed phase of aluminum oxide was investigated. The as-extruded alloy shows an approximate steady-state creep in which the creed rate depends exponentially on the applied stress. The activation energy of creeb is abbroximately 150,000 cal per mole. The recrystallized alloy shows no steady-state creep. ONE method of improving the creep resistance of a metal is to introduce a finely dispersed second phase into the metal matrix. The improvement of the creep resistance has been qualitatively explained by assuming that the dispersed second-phase particles act as obstacles to dislocation motion. If the main effect of second-phase particles is simply to hinder dislocation motion then it is possible to derive a high-temperature creep equation for a dispersion-hardened alloy in a straightforward manner. In the Appendix of this paper such an equation is derived from a creep model which works very well for pure metals. Recently, F. V. Lenel has fabricated, for the first time, powder extrusions of aluminum-aluminum oxide in a large-grained recrystallized form. This alloy, designated as MD 2100, consists of a fine dispersion of aluminum oxide plates in a matrix of commercial purity aluminum. A considerable amount of investigation has been carried out concerning the microstructure and physical properties of this alloy.&apos; ) The aluminum oxide is present in the form of flakes 130A units thick and 0.3 u on edge. They are dispersed in the aluminum matrix with an average spacing of approximately 0.5 jx. The spacing varies in the range of 0.05 to 1.5 µ. The alloy structure is extremely stable at high temperatures. For this reason the alloy offers a unique opportunity for a fundamental study of creep of a very finely dispersed two-phase alloy. Lenel supplied specimens in both the unrecrystallized and recrystallized condition. This paper reports high-temperature creep experiments carried out on these specimens. The results obtained were rather unexpected. No steady-state creep was observed in the recrys-tallized material. In fact, after some transient creep which takes place upon loading, the creep rate is essentially zero ( < 10-8per min). If the second-phase particles acted solely as obstacles to the motion of dislocations, measurable steady-state creep would be expected. Since none is observed it appears that the main effect of the fine dispersion in the recrystallized material is to inactivate the dislocation sources themselves, rather than hinder the motion of dislocation loops created at these sources. EXPERIMENTAL DETAILS Specimens were tested in wire form, 0.087 in. in diam for the as-extruded alloy, and 0.035 in. in diam for the recrystallized alloy. These samples were held in friction-type wire grips; a gage length of 2.5 cm was used for all the creep tests. The specimens were held at 600°C in the test apparatus for at least 15 hr prior to each test. The tests were run under the condition of constant loading and, since the creep strains were small, can be considered as constant stress tests. The temperature of testing was held constant within 3°C. Elongations were measured with an optical cathetometer which was capable of measuring strains as smaIl as 0.00012. This allowed the measurement of strain rates as low as l0-8&apos;per rnin. In addition to the creep tests optical micrographs were made in order to determine both the grain size and microstructure of these materials. RESULTS Fig. 1 shows a few typical creep curves obtained from the as-extruded material. The elongations were somewhat erratic, but each curve shows a region of quasi-steady-state creep from which an approximate steady-state creep rate can be obtained. In general the higher the stress at a given temperature, the greater the total elongation before fracture. The lower the applied stress, the longer is the region where the creep rate is almost constant. Summary data from the creep tests of the as-extruded material are listed in Table I. The steady-state creep data of the as-extruded material for a range of stresses at a constant temperature follow a creep equation of the type creep rate = K&apos; = A exp (&) [11 where A and B are constants, k is Boltzmann&apos;s constant, T is the absolute temperature, and a the stress. The standard error of estimate of the data received is less than one order of magnitude. As shown in Fig. 2, if one compensates the creep-rate data for the effect of temperature over the range of test temperature, the steady-state creep data roughly follow a creep equation of the type Temperature compensated creep rate = K* = A exp

Jan 1, 1960

By W. C. Leslie, R. M. Fisher, K. G. Carroll

A nitride, believed to be Si3N, has been separated from three nitrided silicon steels. Germanium nitride, Ge3N4, has been prepared from pure germanium. Comparison of the diffraction patterns indicates that the two nitrides are isomorphous; on orthorhombic structure is suggested in place of the rhombohedral structure previously reported for Ge3N4. THE possibility that a nitride of silicon may, under appropriate conditions, precipitate in silicon steels or in steels killed with silicon makes it desirable to have some positive means of identifying such a compound. One such means is the X-ray or electron diffraction pattern of the nitride. A review of the meager data in the literature indicates that the nitride most likely to form is Si3N4, a conclusion supported by the results of a study of nitrided silicon steels to be published shortly by L. S. Darken and R. P. Smith, of this Laboratory. Unfortunately, there is available no diffraction pattern for this nitride. Data have been reported, however, for Ge3N4 which, judging from the similarity between germanium and silicon, might be expected to be isomorphous with Si3N4. An effort was made, therefore, to form such a silicon nitride, to determine its composition and diffraction pattern and, if possible, its structure. To this end a series of three silicon steels was nitrided under controlled conditions with the resultant formation of nitride particles which yielded an electron diffraction pattern in situ. The particles were then extracted from the steel and an attempt was made to determine their chemical composition. X-ray and electron diffraction patterns were also obtained from the extracted particles, which indicate that the nitride is isomorphous with Ge3N4, although a complete determination of the structure has not been possible. These results show that a silicon nitride with a well-defined diffraction pattern can form in silicon steels, and they suggest that this nitride is Si3N4. Materials and Procedures The sillicon steels investigated were In the form of thin sheet or strip and had the composition shown in Table I. The 0.58 and 1.21 pct Si steels were nitrided by holding them at 1110°F in an H2-NH3 atmosphere containing 3 pct ammonia for 48 hr. The nitride particle size was increased by subsequent heating at 1500°F for 13 1/2 hr in helium. The resulting microstructure is shown in Fig. 1. The steel containing 3.20 pct Si was nitrided at 1200°F for 16 1/2 hr after which it was held in helium at 1500°F for 4 hr. Its structure as seen under the electron microscope is illustrated by Fig. 2. As would be expected from the higher silicon content and the shorter holding time at 1500 °F, the nitride particles are smaller and more numerous than those in the 1.21 pct Si steel. The ammonia-hydrogen treatment reduced the carbon content of the steels to a very low level, so no interference was encountered from carbon or carbides. In the case of the 3.2 pct Si steel, the carbon was reduced to 0.003 pct before nitriding by heating in dry hydrogen. Attempts to obtain an X-ray diffraction pattern from polished and etched surfaces of the 1.21 and the 3.20 pct Si steels were unsuccessful. However, an electron diffraction pattern was obtained from the surface of the steels. The interplanar spacings obtained from these patterns arc shown in Table 11, col. 5. The nitride particles were then extracted from all three steels by dissolving the ferrite matrix in bromine-methyl acetate, the solution used in the Beeghly method for the extraction of aluminum nitride from steel. X-ray diffraction patterns of these residues, obtained by means of a spectrometer and by a 57 mm Debye-Scherrer powder camera using filtered cobalt or chromium radiation, are given in Table II along with the pattern obtained by

Jan 1, 1953

Organization Place Date 1918 American Chemical Society Cleveland, O. Sept. 9-12 American Society of Sanitary En Engineers Chicago, Ill. Sept. 3-5 National Petroleum Association Atlantic City, N.J. -Sept. American Institute of Mining Engineers Colorado Sept. 2-7 National Association of Stationary Engineers.... Cincinnati, O. Sept. 9-13 Association Iron, Steel, Electrical, Engineers Baltimore, Md. Sept. 9-14 British Iron and Steel Institute, Autumn Meeting London, Eng. Sept. 12-13 National Exposition of Chemical Industries New York, N. Y. Sept. 23-28 American Electrochemical Society Princeton, N. J. Sept. 30- Oct. 2

Jan 9, 1918

Elected Died 1895 *ABBOTT, AI ATTHUR 1908 1882 *ABBOTT, ARTHUR V 1906 1905 * ABE, MASAYOSHI 1909 1903 * ADAMS, CHARLES C. 1905 1905 * ADAMS, WILLAMS 1909 1903 * ADAMS, W. EDWARDS 1910 1884 *ADDY, MATTHEW 1896 1906 * AFFLECK, WILLIAM A. 1911 1889 * AKERS, WILLIAMS 1906 1905 * ALABASTER, RUPPERT C. 1911 1899 * ALBERGER, LOUIS R. 1911 1894 *ALLEN R B 1896 1905 * ALLEN, R. SCOTT 1906 1874 * AMIOT, H. 1892 1886 *AMSLER, CARL 1894 1898 ** ANFERSON, JOHN w. 1905 1895 *ÅNGSTROM, CARL 1901 1887 * ARCHBALD, JAMES 1910 1900 * ARLETT, GEORGE H 1906 1895 *ARMSTRONG, JOHN F 1898 1882 *ARNOLDS, HUGO 1886 1875 *ASHBURNER, CHARLES A 1889 1872 *ASIIBURNER, WILLIAM 1887 1883 *ATKINS, C M , JR 1885 1905 * AUSTEN, PETER T 1907

Jan 1, 1917

By A. Gittens

In two recent papers stevens13,14 has compared the methods used by various investigators to calculate the contribution of grain boundary sliding to the total creep strain. In previous work Gittins15 has shown that the strain due to grain boundary sliding Egb may be estimated from the lateral, d, and vertical, v, displacements of a longitudinal marker line as it crosses a grain boundary. He obtained the formula, where nL is the number of grains per unit length measured on the specimens before creep, and \p and ?2 are, respectively, the angle between the grain boundary and the stress axis in the plane of the surface and normal to the surface (see Ref. 13, Fig. 1). The subscript L indicates that observations are made in a longitudinal direction parallel to the stress axis. It was generally found more convenient to measure the grain size of a specimen before creep; this was necessary to characterize the specimen. Stevens13,14 however prefers to define Egb in terms of NL, the number of grains per unit length after creep. Since nL - NL(l + €1) where cr is the total strain, Eq. 1 11 becomes The quantities d and ?, can be determined directly from the marker lines, while v and ?2 are found by sectioning normal to the surface. In the interior when symmetry considerations suggest that v = d and ?1 - ?2 the strain due to grain boundary sliding may be estimated from a suitable internal longitudinal marker line by the equation To determine cgb at the surface using either Eqs. |1| or [2] requires a large number of observations, particularly if many estimates of cgb are required, and also it is impossible to determine the variation of cgh with creep strain on the same specimen because the specimen must be sectioned to determine ?2. Gittins15 found that for a number of materials the sliding vectors d and v were related to each other so that provided one was measured the other could be estimated. Also during creep, grain boundaries tend to migrate to meet the surface at angles close to 90 deg,16 so that the term nL(v/tan?2)L was comparatively small when 4,- 90 deg. By determining the frequency distributions of ?2 on control specimens this term can be estimated without sectioning the creep specimen. In this way an empirical equation based on Eqs. |1| and |2| enables cgb to be determined with reasonable accuracy with fewer observations of the angles and sliding components. For B brass, the relationship between the sliding vectors indicated that ceb = 0.85nLVL . In Table I of Stevens paper this equation is stated to be incorrectly derived. However it should be pointed out that this is an empirical equation derived from Eq. |1|, based on a knowledge of the relationship between d and v and on the frequency distributions of ?1 and ?2 for a particular material under given experimental conditions. It was used only when these relationships were known, to reduce the number of observations required to estimate cb. Therefore the comment "derivation incorrect does not apply. Gittins did in fact make use of Eqs. |1| and 131. Author&apos;s Reply I must apologize to Dr. Gittins for the inadvertent misrepresentation of his work. Other slight errors in Table I have been pointed out to me. Langdon (No. 12 Table I), Gifkins (No. 7, Table I), and possibly other workers did not measure the number of boundaries per unit length after creep (A&apos;) but the corresponding quantity bejove creep (n). As Dr. Gittins points out, a completely analogous set of equations to those given in the paper can be derived by the same method: using the number of boundaries per unit length before instead of after creep. The basic equations corresponding to Eqs. [2] and 171 of the paper, from which all the others can be derived, are

Jan 1, 1968