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By D. E. Peacock, B. Harris

Thermal-expansion and electrical-resistivity measurements have been carried out below 400°K on niobium and two niobium alloys containing tungsten. For anonaly in the expansion us temperature curve below aboct 300°K. This reslt is consistent with an earlier obsercation that Young's modilus joy Cb-132 lms an unusiully strong -tenperati-e dependence below roon temperature. No anonulous behavior was observed in the resistiuity vs temperature curve for either alloy or in the magnetic susceptibility us tenperature curve for Cb-132. These results are disclssed in terms of various electronic and bonding theories of the transition metals and their alloys, but it has not been possible to reach any definite conclusion as to the cause of the results obtained. ALONG with investigations of the low-temperature mechanical behavior of niobium and its alloys, some of the physical properties of these materials have also been studied. In the work described here, thermal expansion and electrical resistivity were measured below 400°K for niobium and two of its alloys, Cb-132 and D-43. In addition, the magnetic susceptibility of Cb-132 was measured over the same temperature range. The alloys are representative of two distinct tion-hardened alloy such as might find service as a turbine blade, while D-43 (Nb, 5.3 at. pct W, 1.1 at. pct Zr. and 0.08 at. pct C) is a solution- and dispersion-hardened alloy, of considerably lower strength than Cb-132. which is a potential vane material. Their significant common feature is the presence of tungsten as the principal source of solution hardening. EXPERIMENTAL TECHNIQUES Thermal-expansion measurements were made with a quartz-tube dilatometer using baths of liquid nitrogen, liquid bromoethane, and a liquid polyalkylene glycol derivative to cover the range 80 to 400 K. Results are recorded as expansion relative to that of quartz, and the probable maximum error in any value of relative expansion. All, is about il pct. The metallurgical condition of the specimens, which were in rod form. will be discussed in the section dealing with experimental results. Resistivity was measured on recrystallized wires 0.030 in. in diam using a potentiometric technique. The same baths were used for temperatures between 80' and 400°K as were used for the expansion measurements. and in addition the resistance of D-43 and Cb-132 was measured at 4.2 K by immersion in liquid helium. The maximum expected experimental error in any resistivity value is about 3 pct and that in any change in resistivity about i0.05 pct. Temperatures in both sets of experiments were measured with liquid-in-glass thermometers with an accuracy usually better than 1°K. EXPERIMENTAL RESULTS 1) Thermal Expansion. In Fig. 1 is shown the relative linear expansion of recrystallized niobium. D-43. and Cb-132. The curve for Cb-132 is composed of results from several runs on three different samples. Two of the samples were annealed for an hour at 1500°C to cause recrystallization and the third was annealed for an hour at 2000'C to remove some mi-crosegregation of tungsten which was known to be present in the wrought alloy received from the manu-

Jan 1, 1967

By W. G. Pfann

In zone-melting, a small molten zone or zones traverse a long charge of alloy or impure metal. Consequences of this manner of freezing are examined with impurerespect to solute distribution in the ingot, with particular reference to purification and to prevention of segregation. Results are expressed in terms of the number, size, and direction of travel of the zones, the initial intermsofsolute distribution, and the distribution coefficient. IF a charge of binary solid-solution alloy is melted and then frozen slowly from one end, as for example in the Bridgman method of making single crystals,' coring usually occurs, with a resulting end-to-end variation in concentration. Such coring, or normal segregation, is undesirable where uniformity is an object. On the other hand, for certain systems, it can be utilized to refine a material by concentrating impurities at one end of the ingot.'. ' In the present paper a different manner of freezing will be examined with respect to the distribution of solute in the ingot. A number of procedures will be indicated which have in common the traversal of a relatively long charge of solid alloy by a small molten zone. Such methods will be denoted by the general term zone-,melting, while the process described in the preceding paragraph will be called normal freezing. It will be shown that, in contrast to normal freezing, zone-melting affords wide latitude in possible distributions of solute. Segregation can either be almost entirely eliminated or it can be enhanced so as to provide a high degree of sttparation of solute and solvent. A number of simplifying assumptions will be invoked which, while not entirely realizable in practice, nevertheless provide a suitable point of departure for more refined treatments. Moreover, our own experience with zone-melting has shown that, for certain systems at least, the analysis holds quite well. The present paper will be confined to a discussion of principles and a general description of procedures. Comparison with experiment is planned for later publication. Normal Freezing Before considering zone-melting, segregation during normal freezing will be reviewed briefly. If a cylinder of molten binary alloy is made to freeze from one end as in Fig. 1, there usually will be a segregating action which will concentrate the solute in one or the other end of the ingot. If the constitutional diagram for the system is like that of Fig. 2, then the distribution coefficient k, defined as the ratio of the concentration in the solid to that in the liquid at equilibrium, will be less than one and the solute will be concentrated in the last regions to freeze. If the solute raises the freezing point, then k will be greater than one and the solute will be concentrated in the first regions to freeze. The concentration in the solid as a function of g, the fraction which has solidified, can be expressed by the relation: C = kC0 (1-g)k-1 [I] where C, is the initial solute concentration in the melt. Eq 1 is based on the following assumptions: 1—Diffusion in the solid is negligible. 2—Diffusion in the liquid is complete (i.e., concentration in the liquid is uniform). 3—k is constant. Concentration curves representing eq 1 for k's from 0.01 to 5.0 are plotted in Fig. 3. This equation, in one form or another, has been treated by Gulliver,³ Scheuer,4 Hayes and Chipman5 for alloys and by McFee2 for NaCl crystals. It is derived in Appendix I. It should be pointed out that the k which is calculated from the phase diagram will be valid only in the ideal case for which the stated assumptions are correct. In all actual cases, the effective k will be larger than this value for solutes which lower the melting point, smaller for solutes which raise the melting point, and will probably vary during the beginning of the freezing process. For simplification it will be assumed that the ideal k is valid. Zone-Leveling Processes The processes of this part are designed to produce a uniform, or level, distribution of solute in the ingot. Single Pass: Consider a rod or charge of alloy whose cross-section is constant and whose composition, C2, is constant, although permissibly varying on a microscopic scale." Such a charge might be a rapidly frozen casting or a mixture of crushed or powdered constituents. Cause a molten zone of

Jan 1, 1953

By R. L. McCarron, G. R. Belton

The diffusivities of oxygen and sulfur in liquid iron have heen determined hy a capillary technique in which the surface concentrations of the solutes were established by means of appropriate H2/H2 and H2S/H, gas mixtures. Total diffusate and concentration profile results are shown to be in good accord, yielding for- 1560 and Supporting results at 1660°C are also presented. The conditions necessary to avoid gas transport control in this type of experiment are discussed. IN spite of their importance in understanding the kinetics and mechanisms of refining reactions, the dif-fusivities of oxygen and sulfur in liquid iron are not well established. Accordingly, as a first step in studies of rates of solute absorption from the gas phase into liquid iron, new measurements of these diffusivities have been made and are presented in this paper. The only published results for the diffusion of sulfur in pure liquid iron are those of Kawai.' He used a diffusion couple technique in which two cylindrical specimens, one containing sulfur and the other with negligible sulfur concentration, were joined together and held in a refractory capillary. After an experiment, the sample was quenched and the concentration distribution of the solute determined. Kawai recognized that significant changes in solute distribution occurred during melting and freezing and he attempted to correct the concentration profiles for these effects to give a sulfur diffusivity of 4.6 x 10-6 sq cm per sec at 1560°C. The method of correction, however, was not rigorous and the uncertainty in this result cannot be easily assessed. Koslov et a1.2 have reported the diffusivity of oxygen in iron as 7.8 x 10"3 sq cm per sec at 1660°C. This value appears to be unreasonably high but, unfortunately, details of their experiments are not available. Shurygin and Kryuk have used the rotating disc method for a study of oxygen diffusion in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was determined by measuring the decrease in weight of the disc. On the assumption that the rate of dissolution was controlled by the diffusion of oxygen in the iron, the diffusion coefficient was computed to be 5.2 x sq cm per sec at 1550°C. However, the Levich equation, which was used to interpret the rate data, was originally de- rived for the case of mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich's equations. Recently, Novokhatskiy and Ershov, using an identical experimental method to that of Shurygin and Kryuk, obtained a diffusivity for oxygen in liquid iron of 1.22 x 104 sq cm per sec at 1550°C: no reasons were offered for the disagreement. Schwerdtfeger5 has also recently studied the diffusivity of oxygen in liquid iron. He reacted shallow melts of liquid iron, 0.5 to 1.0 cm deep and contained in high-purity alumina crucibles, with appropriate H20-HZ-He mixtures. The total sample was analyzed, without sectioning, to obtain the average concentration of diffusate. A value at 1610°C of D = 12(3) x 10-5 sq cm per sec was obtained from the results of twenty experiments.= Oxygen profile measurements, which were carried out in three additional experiments using long capillaries and the semiinfinite boundary conditions, indicated a diffusivity about half that computed from the shallow bath experiments. Possible sources of error in Schwerdtfeger's study will be discussed later in this paper. EXPERIMENTAL TECHNIQUE The essential arrangement of the diffusion cell is shown in Fig. 1. The liquid iron was contained in an alumina capillary, 3 to 4 mm diam and 3 to 9 cm long, which was supported by a hollow alumina pedestal and this whole assembly was held within a movable alumina reaction tube. This tube, which was about 7 mm in bore

Jan 1, 1970

By G. W. Josephson

JUDGING by the progressive atmosphere prevailing in the nonmetallic mineral industries during the past year, postwar conditions were healthful though inflationary. Demand for most industrial mineral products has been exceptionally high and many new production records were attained. Severe shortages of some commodities existed, especially building materials and fertilizers. Production costs and prices increased and profitable operation was general. Under these conditions expansion programs were the order of the day. Ample funds were available to finance the purchase of good equipment; and, as wages and other operating costs were increasing, primary emphasis was placed on attaining maximum efficiency in new installations. These efforts were hampered by shortages and slow delivery of desirable equipment, so compromises in design were often necessary. However, on the whole, production practice improved.

Jan 1, 1948

By B. C. Allen

Surface free energy and surface self-diffusion of solid molybdenum were studied in the temperature range 1600" to 2400°C using pressure-sintered bi-crystals. Comparison of groove angles formed in various surfaces perpendicular to the grain boundary indicate a maximum of 1 pct variation in surface free energy with crystallographic mientation. This anisotropy tends to decrease with increasing temperature. The surface diffusion of the bicrystals is equivalent to that of sheet with a mild (100) Preferred orientation. Anomalously low values found for bi-crystals with surface orientations of (OOl), (012), and (011) are rationalized in terms of anisotropy in surface free energy. THE effect of crystallographic orientation on surface free energy1,' and surface self-diffusion3,4 has been primarily studied in fcc metals. The object of this work was to study the effect of orientation on surface diffusion and surface free energy of bcc molybdenum using pressure-sintered bicrystals. EXPERIMENTAL WORK Materials and Crystal Preparation. Arc-melted molybdenum rod was obtained commercially and electron beam zone refined at 50 cm per hr at 10- 5 torr to form single crystals about 8 cm long and 0.65 cm diam. Three crystals were prepared with axial orientations about 1 deg from [001.], [011], and. [111]. To reduce the carbon content, the crystals were annealed 2 hr in 1.4 atm flowing wet hydrogen at 2050°C. Then the oxygen content was reduced by annealing for 2 hr in -30°C dewpoint hydrogen at 2020°C. The resulting impurity analysis is given in Table I. Bicrystal Preparation. The single crystal rods were cut into transverse slices with a thin silicon carbide abrasive wheel to produce specimens about 0.6 cm long. They were mounted in epoxy and surrounded by stainless steel washers. Cutting in half was done longitudinally at various angles to known crystallographic planes containing the cylinder axis according to Fig. 1. To reduce surface deformation resulting from the cutoff wheel and thus reduce parasitic grain boundary formation on subsequent annealing, about 0.003 cm was manually ground off each cut surface with 600 grit paper. Care was taken to keep the surface flat. After removal from the mounts, one half was generally ro-tated 180 deg with respect to the other to give a po- tential symmetrical tilt grain boundary between the two halves. In the other cases when low misorienta-tion angles were desired, the crystals were not rotated. On the basis of symmetry, sufficient bicrystals were prepared to cover the entire range of misorientations for symmetrical tilt boundaries. The misorientations, +, ranged from 0 to 45, 0 to 90, and 0 to 60 deg for [001], [011], and [111] bicrystals, respectively. One [Ill] twist bicrystal was prepared from 2 single crystal discs rotated 17 deg relative to each other. Each specimen consisted of two pieces which were placed in a cylindrical tantalum can. Sharp edges were rounded and the fit was made as snug as possible to reduce subsequent deformation during bonding. The assembly and crystals generally were vicuum outgassed at 900" or 1700°C and then electron beam welded in the can at l x 10-4 torr. After being leak checked, the samples were placed in an autoclave and hydrostatically gas-pressure bonded5 in four batches under helium at 10,000 to 18,000 psi at 1650°C for 3 hr. Satisfactory bonds were obtained in many cases, and most of the crystals bonded after two exposures. The results did not appear to be affected by the various pressures used, preannealing conditions, crystal orientation, or time-pressure-temperature route taken to the final bonding condition. After bonding, the tantalum cans were selectively removed in cold concentrated HF. Measurements indicated overall deformation was under 1 pct. The bicrystals were metallographically ground and polished flat and perpendicular to the axis. Examination showed the boundaries were straight and almost free of parasitic grains caused by extraneous local deformation. Annealing. In preparation for thermal grooving, the bicrystals were cleaned and annealed by outgassing at 10-5 torr at 1900°C and heating at 2300°C under 1 atm 99.996 Ar for 0.5 hr. The crystals were held in a closed 4-deck box made of molybdenum sheet, and were heated in a Ta-1OW resistance furnace. The ar-

Jan 1, 1970

By L. H Levenson, Charles S. Barrett

The orientation of metal crystals and grains, both large and small, can be detcrmined conveniently and accurately without the use of X-ray apparatus. This seems to be appreciated by so few metallurgists that it may be useful to explain in detail the method we have found most satisfactory in the laboratory—the reflection of light from crystallographie etch pits. This note includes a description of a suitable inexpensive instrument and instructions for etching various metals and for plotting the data. As the stereographie projection is used to facilitate handling the data, this note may he considered as an appendix to an earlier review of the metallurgical uses of the stercographie projection.' Various methods involving etch pits have been used by other investigators. Bridgman's method2 consists of attaching the specimen to a sphere (a transparent sphere is convenient4 , holding it at arm's length, and marking a spot on it when it has been turned so that the eteh pits reflect light into the eye of the observer from a lamp standing behind him. It has an accuracy of about 2" and is extrernely rapid. A greater accuracy can be obtained by having the reflected light fall on a screen, as has been done by Czochralski,5 Chalmers,6 and Schubnikov.7 All of these methods have been intended for undeformed single crystals. Tammann and his coworkers3,8 developed a method for estimating the number of grains in a polyerystalline aggregate having orientations in a given region of the stereographic triangle and thus obtained statistical information about deformation and reerystallization textures. While the method has had some use in recent years,9 it is not applicable to the majority of problems in physical metallurgy. Smith and Mehl10 determined orientations by plotting the directions of the sides of individual etch pits on a stereographic projection. The accuracy is limited to about 3" and the method requires careful polishing and high magnification.

Jan 1, 1940

By Charles S. Barrett, L. H. Levenson

The orientation of metal crystals and grains, both large and small, can be detcrmined conveniently and accurately without the use of X-ray apparatus. This seems to be appreciated by so few metallurgists that it may be useful to explain in detail the method we have found most satisfactory in the laboratory—the reflection of light from crystallographie etch pits. This note includes a description of a suitable inexpensive instrument and instructions for etching various metals and for plotting the data. As the stereographie projection is used to facilitate handling the data, this note may he considered as an appendix to an earlier review of the metallurgical uses of the stercographie projection.' Various methods involving etch pits have been used by other investigators. Bridgman's method2 consists of attaching the specimen to a sphere (a transparent sphere is convenient4 , holding it at arm's length, and marking a spot on it when it has been turned so that the eteh pits reflect light into the eye of the observer from a lamp standing behind him. It has an accuracy of about 2" and is extrernely rapid. A greater accuracy can be obtained by having the reflected light fall on a screen, as has been done by Czochralski,5 Chalmers,6 and Schubnikov.7 All of these methods have been intended for undeformed single crystals. Tammann and his coworkers3,8 developed a method for estimating the number of grains in a polyerystalline aggregate having orientations in a given region of the stereographic triangle and thus obtained statistical information about deformation and reerystallization textures. While the method has had some use in recent years,9 it is not applicable to the majority of problems in physical metallurgy. Smith and Mehl10 determined orientations by plotting the directions of the sides of individual etch pits on a stereographic projection. The accuracy is limited to about 3" and the method requires careful polishing and high magnification.

Jan 1, 1940

By B. D. Lichter

The lattice parameters of zirconium and zirconium-oxygen solid solutions (hcp) were determined from measurements of back-reflection X-ray photograms obtained at 29°C using a symmetrical focussing camera. The following linear equations between parameters (c,a) in angstrom units (10-8 cm) and atom ratio (m) of oxygen to zirconium were obtained: c = 5.14764 + 0.2077m a =3.23168 + 0.1099m. The linear equations given are valid over the range 0 to 5 at. Pct 0. The accuracy of individual parameter measurements approaches the limiting accuracy determined by the spectral broadening of the incident characteristic radiation, and exceeds the accuracy of previously reported values. THE present work was undertaken in order to determine the lattice parameters of zirconium-oxygen solid solutions with an accuracy that allows quantitative determination of oxygen in zirconium. The results indicate that this is possible if very careful measurements are made, since the parameter change is only a few hundredths of a percent per at. pct 0.1, 2 In the present investigation the desired accuracy was achieved with large-grained samples using a back-reflection focussing camera and maintaining good temperature control during exposure. In addition a digital computer was used for calculation of the parameters by means of an analytical extrapolation.37 Suitable diffraction photograms were obtained from large-grained samples by using a modification of the technique described by Graf and Monteil.5 This consists of simultaneous rotation and oscillation of the specimen about two mutually perpendicular axes during exposure. Whereas, normally the upper limit of grain size is about 50 µ for useable diffraction photograms, this technique allows extending the upper limit of grain-size to exposure of a single crystal. EXPERIMENTAL Preparation of Alloys for X-ray Diffraction—Zir-conium, designated as hafnium-free, Westinghouse "Grade 1," was swaged from l/2-in.-diam crystal bar to 3/8-in.-diam rods. Substantially all of the hydrogen was removed from the zirconium by annealing at 1200°C in a high dynamic vacuum. The rods were then swaged to 0.2 in. diam without intermediate annealing, and 2 in. lengths were cut for alloying with oxygen. Samples for chemical analysis were taken from portions of the rods between each 2 in. length. Chemical analysis of the dehydroge-nated zirconium is given in Table I. Commercial tank oxygen (99.5 pct 0) was condensed in a liquid nitrogen-cooled trap, and part of the condensate was slowly reevaporated into 5-liter storage flasks. Nitrogen remained as a reactive impurity, and the calculated maximum increase in nitrogen content after a 5 at. pct 0 addition to zirconium was 50 ppm by weight. However, chemical analyses of several of the prepared alloys indicated that the maximum increase in nitrogen content was 10 ppm. The storage flasks, a Sieverts-type gas burette and manometer, and associated traps, pumps, and pressure gauges were connected through a glass high-vacuum manifold to comprise the gas addition system. A fused silica tube, connected to the mani-

Jan 1, 1961

By Axel Sahlin

Jan 1, 1898

By Jean Herenguel

THE published work of Lacombe and Beaujard' has demonstrated the interesting application of etch figures to the determination of crystal orientations in aluminum by a purely micrographic method. The geometry of these figures leaves no ambiguity and the method has the added advantage of being applicable to very small crystal units. These authors applied the technique to the study of high purity aluminum, and it has now been adopted buy Heren-guel and his collaborators to various researches on commercial aluminum, containing up to 1 pct Fe and Si. This must modify the opinion point,ed out by

Jan 1, 1953

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Jan 1, 1907

By J. R. Finlay

BEFORE entering into the statistical part of this article, some general comments may be ln order. Each important war seems to introduce a new atmosphere and a new epoch. The Civil War led to the period of great interior development in North America, of the transcontinental railroads, and of large-scale manufactures. The first World War introduced the general use of the automobile, the building of a huge network of highways, the radio, and household engineering. Now I expect World War II also to introduce some new ways of living. Transocean aviation will become a commonplace; we shall probably have much more of an eye to our military and naval establishments and be more conscious of Eastern Hemisphere affairs instead of thinking so exclusively of the Western. Each war has also multiplied government expenditures and taxes; and to this rule the present one will certainly be no exception.

Jan 1, 1944

By A. C. Fieldner, W. A. Selvig

For purposes of coal classification it is desirable to know the composition and calorific value of the pure coal substance; that is, of the coal free from its ash-forming minerals. Two methods suggest themselves: (1) To free the coal from most of the ash-forming material previous to the analysis; and (2) to analyze the coal as received and calculate the analysis, with certain more or less arbitrary corrections, to the pure-coal basis. Calculation methods are obviously more apt to give correct results with low-ash than high-ash coals. With coals of unusually high ash it would appear preferable to remove, previous to the analysis, as much of the inorganic matter as possible, by float-and-sink or acid-treating methods. Effect of Ignition on Inorganic Constituents of Coal The need of corrections in calculating analysis to the pure-coal basis is due to the fact that the ash, as determined by ignition, is not the same, in either weight or composition, as the inorganic mineral matter in the coal. On ignition a number of changes occur in the coal such as loss of water of hydration of the shaly material, conversion of pyrite (FeS2) to ferric oxide (Fe203) with evolution of the sulfur as sulfur dioxide or possible fixation of more or less of the sulfur in the ash as calcium sulfate (CaSO4), and decomposition of calcite (CaC03) to calcium oxide (CaO). The amount of sulfur from pyrite which remains in the ash as calcium sulfate depends on the amount of calcite and pyrite in the coal. Certain coals high in both calcite and pyrite show relatively large amounts of sulfate sulfur in the coal ash. The determination of total carbon and hydrogen in coal includes, besides the organic carbon and hydrogen, the carbon of inorganic carbonates such as calcite, and the hydrogen of the water of composition of some of the ash-forming minerals. For detailed discussion of corrections proposed for calculations of coal analyses to the " pure "

Jan 1, 1930

Bailey, Lewis Newton, Master Engineer, Senior Grade, 4th Regiment, U. S. Engineers, Headquarters Company, died of pneumonia at Camp Merritt, N. J., on April 30, 1918. Baird, Louis, Lieut., Royal Field Artillery, British Army, died on the battlefield in 1915. Cobeldick, William Morley, Royal Engineers, died from gas poisoning on October 7, 1915. Dougall, Ralph, killed in action. Evans, Alfred Winter, Lieut.-Col., New Zealand Rifle Brigade, D. S. 0., D. C. M., killed in action on October 12, 1917. Gorman, Thomas C., Lieut., Canadian Engineers, killed in France, Mar. 18, 1918. Hague, William, 1st Lieut., Engineer Officers' Reserve Corps, died in active service. Hall, William T., Capt., Royal Flying Corps, killed in action. Heine, Bernhardt E., Lieut., Aviation Service, killed at Fort Sill, Okla., Aug. 10, 1918. Irving, John Duer, Capt., 11th Engineers, A. E. F., died while on active service in France on July 26, 1918.

Jan 9, 1918

By B. W. Prof. Frazier

I PROPOSE in this paper to treat of the chimney merely as a heat engine, as one of the devices resorted to in practice for the conversion of heat into mechanical work. For the sake of simplicity and clearness in the discussion, let us consider the subject in its simplest form. Conceive a chamber, heated from without, in free communicatioH at one end with the external atmosphere, and at the other end opening into a vertical chimney. Let the. cross-section of the chamber be so great, relatively to that of the chimney, that we can neglect the actual energy of the air passing through the chamber. We will neglect, also, all passive resistances to the passage of the air. We will assume that the cross-section of the chimney is constant, and that the air in passing through it neither gains nor loses heat. The following symbols will be employed in the discussion : Po = the normal pressure of the atmosphere, which, it is assumed, is the pressure existing at the level of the chamber. Po = 10332.96 kilograms per square meter. P2 = the pressure of the external atmosphere at the top of the chimney. To = the, absolute temperature of melting ice by the centigrade scale. This is assumed to be the temperature of the external air at the level of the chamber. To = 273°. T2 =the absolute temperature of the air as it passes from the chamber to the chimney. T3 =the absolute temperature of the air as it issues from the chimney. to, t2, t3 are the temperatures, as recorded on the centigrade ther¬mometer, corresponding to the absolute temperatures To, T2, T3 re-spectively to = 0° C. In general, t = T- 273. Io, I2, I3, represent the intrinsic energy of the air at the temperatures To, T2, T3 respectively.

Jan 1, 1882

By R. J. Lloyd

INTRODUCTION The Mount Isa Mine is a large modern underground mine located in North-Western Queensland, Australia. Two ore types are mined and treated separately. Currently silver-lead-zinc ore is mined at the rate of 2.6 million tonnes per annum and copper ore at the rate of 4.6 million tonnes per annum. The silver-lead-zinc orebodies are mined by sub level open stoping and cut and fill methods whilst all copper ore is extracted by various forms of sub level open stoping. The mining operations are highly mechanised and utilise diesel powered load-haul-dump units of various sizes, two and three boom face drilling jumbos, electric-hydraulic rotary-percussive ring drills, in-the-hole hammer drills, rotary blasthole drills, raiseborers, battery/trolley locomotives, a large fleet of rubber tyred service and supply vehicles plus light rockdrills mounted on airlegs, rail mounted overshot shovels and battery and diesel powered locomotives. All stoping production ore is extracted with diesel powered load-haul-dump units. The ore is tipped into orepasses which connect to the main rail haulage levels. On the haulage levels electric battery/trolley locomotives are used to pull rakes of bottom dump or side dump trucks which feed the ore into primary crushers. Following two stage crushing the ore is conveyed to the shaft and hoistod to surface in bottom dump skips. Each ore stream has its own rail transport system, crushing stations and hoisting shaft feeding separate concentrators. This paper will consider some aspects of the role of equipment and machinery in the growth of the mine, will discuss in some detail the machinery and equipment in use today and will conclude with a look at some possible developments in mining equipment for the future, with particular reference to the Mount Isa Mine. A summary of mining equipment in use at Mount Isa is given in the Appendix. THE PAST Silver-lead-zinc ore was discovered at Mount Isa in 1923 and within a very short time many small mines were being developed. However the rich surface ore traces did not continue and by 1928 Mount Isa Mines Limited had acquired sufficient leases to plan for a large scale mine to exploit the low grade orebodies. At this early stage it was recognised that the mine would need to adopt the most mechanised mining techniques then available in order to overcome its twin disadvantages of low graaes and extreme remoteness. The Company introduced bar mounted drifters and overshot shovels to replace hammer and tap and hand shovelling in development work and by 1930 headings were advancing at the rate of 30 metres per week. In keeping with the concept of mechanisation the early engineers designed the Man and Supply shaft with a very large, for those days, cage compartment measuring 3.8 m x 3.4 m. This shaft was the main means of access into the mine for 36 years until the K57 shaft (now R62 shaft) was commissioned in 1966. Man and Supply is still in regular use. Production commenced in 1931 at an annual rate of approximately 660 000 tonnes of silver-lead-zinc ore. The mine was mechanised to an extent which was previously unknown in Australia; whilst the concentrator, smelter and power house utilised the most modern and efficient equipment available. Even so, the mine was very near to closure on several occasions and did not return a dividend to its shareholders for many years. Production levels remained at or slightly below 660 000 tonnes until a separate copper ore streani and mill was commissioned in 1953, doubling the existing production levels. The first underground crushers were installed at this time. Production rates expanded in the years between 1953 and 1973. By 1960 production reached 2740 000 tonnes of ore. In 1965-66 total production was 3650 000 tonnes and in 1973 the production rate plateaued at the current level.

Jan 1, 1981

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

HE high vapor pressures of metals such as lead, calcium, lithium, bismuth, and magnesium at steel-making temperatures present experimental problems which have thus far rendered it almost impossible to obtain really reliable data for their solubilities in liquid iron. Many investigators have attempted to equilibrate liquid iron in the same crucible with the undissolved liquid phase of such volatile metals. The published results,l-6 although useful, are often questionable on the grounds of not being obtained under true equilibrium conditions. Such information is not always of practical value in any case since the equilibrium vapor pressure is often several atmospheres and steel is not currently made at these pressures. Solubility measurements at lower partial pressures (< 1 atm) appeared to be more practical and easier to make. These data could be used to calculate solubilities at other pressures where Henry&apos;s Law is obeyed, and to estimate solubilities under other conditions of temperature and pressure with useful accuracy. This note outlines the development of a general technique for the measurement of solubilities in systems of this kind. The method involves equilibration of the high-boiling metal at known temperatures with the vapors of a low-boiling metal at known partial pressures. Analyses of quenched samples provide vapor pressure-solubility data and make calculations of alloy thermodynamics possible. The principle involved is similar to the closed-system diffusion-transport method which is difficult to apply with most high-melting liquid metals like iron, due to closure problems. A two-zone horizontal (molybdenum wire element) tube furnace, Fig. 1, provides two constant-temperature zones in a reaction tuve (3/4 in. ID by 1 in. OD by 36 in.). A high-boiling metal sample, 9, introduced in the higher-temperature zone, is maintained at temperature T1, and a volatile metal sample, 7, in the lower-temperature zone, is held at T2. A stream of argon with 10 pct hydrogen is passed via flowmeters, 1, and mixing-drying towers, 2 and 3. through the reaction tube at a favorable flowrate and acts as a carrier gas which entrains vapor from the volatile liquid metal at a specific constant partial pressure. The gas mixture passes through a system of constrictions, 6 and 8, to the higher-temperature zone, establishes intimate contact with the high-boiling liquid sample, 9, and exits through a small condenser tube. The entire system is at (nearly) atmospheric pressure and the volume of carrier gas passed is measured with a wet gas meter. When the high-boiling sample attains equilibrium with the vapor phase, both samples are removed and quenched. Analysis of the high-boiling sample for solute content reveals its solubility for the low-boiling metal at a vapor pressure calculated from carrier-gas volume and either a) weight loss of volatile metal or 6) weight gain of high-boiling sample plus condenser (which collects the undissolved vapors). To test the capabilities of the method, liquid silver at 1403&apos;C was equilibrated with lead vapor at various partial pressures. The relatively simple Pb-Ag system was particularly suitable for uncovering experimental problems and providing the first step toward investigations with more volatile metals and more difficult combinations.

Jan 1, 1965

By Ken-ichi Hirano, B. L. Averbach, Morris Cohen, N. Ujiiye

The influence of plastic deformation in compression on the self-diffisivity of a iron has been measured in the temperature range of 742º to 885°C. The diffusivity is enhanced in proportion to the strain rate, but this dependence decreases with increasing temperature. The magnitude of the strain is relatively unimportant in this connection. Strain rates from 0 to -2 x 10-3 sec-1 were investigated, with a corresponding increase in diffusivity up to 3 x 103 times. The results are analyzed in terms of vacancy diffusion and the excess vacancies introduced during dejornzntion. It is concluded that grain boundaries are the main vacancy sinks in polycrystalline iron and that the vacancy lifetime is therefore dependent on the grain size. A typical vacancy lifetime at 800°C with a nzean grain-boundary intercept of 0.3 cm is of the order of 1 sec. LATTICE imperfections are considered to be the dominant mechanism of diffusion in close-packed crystals. Vacant lattice sites are usually the most important defect, but the enhancement of diffusion along grain boundaries and other short-circuiting paths has been well documented. Inasmuch as plastic straining produces a variety of defects, it would be expected that the application of stresses sufficient to cause plastic flow during a diffusion run might result in an increase in the self-diffusivity. Enhanced self-diffusion in a iron under compressive creep has been observed by Buffington and Cohen&apos; and subsequent coworkers.2 Lee and Maddin3,4 have also found an enhancement in the self-diffusivity of silver single crystals undergoing torsional deformation. On the other hand, Darby, Tomizuka, and Balluffi5 have not observed any significant diffusion increase in single crystals of silver deformed either in tension or in compression, although the results in this case may have been affected by the occurrence of recrystallization. With poly crystalline silver, however, Forestieri and Girifalco6 have found en- hanced diffusion during compressive creep. A small decrease in the self-diffusivity of zinc single crystals under compressive loading has been reported,7 but the applied stresses in these experiments were too low to cause appreciable plastic deformation. For the cases in which enhanced diffusion has been found, a number of common effects have been noted. Usually, the ratio of the diffusivity during straining, Ds, to the diffusivity in the unstrained condition, D,, varies linearly with the strain rate, and does not seem to be a function of the plastic strain, at least up to ? = 0.2. Values of Ds/Du of the order of 100 have been reported&apos;-4 but the enhancement decreases with increasing diffusion temperature. The activation energy for diffusion decreases markedly with increasing strain rate and approaches a level of roughly one-half the unstrained value. Most of the current explanations of these observations assume that excess vacancies are generated by the deformation, but rather large concentrations of excess vacancies and/or long lifetimes are required by these theories.&apos;,&apos;,&apos;,&apos; Since the original work on iron, there has been an important improvement in the compressive-loading technique.2 The early data were also analyzed without taking into account the motion of the coordinate system in the specimens undergoing plastic deformation. This problem has now been solved by a number of investigators (see Refs. 11, 12, and the appendix of the present paper). Consequently, the strain-diffusion runs on iron for the Ds measurements were repeated and extended over wider ranges of temperature and strain rate. In addition, the original diffusivity data9 on the unstrained iron have been corrected for the divergence of the beam in the counting system and new data points have been added, resulting in somewhat different values for the self-diffusi-vities in a iron.10 The new values for Du are used in this paper. A comparison of Ds and Du confirms the large enhancement in the self-diffusivity of iron during compressive creep, as previously reported.&apos;,2

Jan 1, 1963

Institute of Metals Division Ferrous and Nonferrous Physical Metallurgy Established as a Division April 26, 1918 (Bylaws published In the 1944 TRANSACTIONS Volume of the Division) A A SMITH, JR, Chairman E A ANDERSON, Past-Chairman F N RHINES, Senior Vice-Chairman W A DEAN, Vice-Chairman H A MALONEY, Treasurer ERNEST KIRKENDALL, Secretary 29 West 39th Street, New York 18, N Y Executive Committee R M BRICK 2 W A JOHNSON 1 H I DIXON 2 E W PALMER 1 M GENSAMER 2 J H SCAFF 3 J D HANAWALT 1 J D SULLIVAN 3

Jan 1, 1952

By L. Kaufman

An equation is derived relating AF a", the difference in free energy between austenite and martensite, to temperature and composition in the iron-chrmnium and iron-chromium -nickel systems. This equation is used to calculate at M,for low-carbon stainless steels. A method for utilizing the energetic equations to calculate M, in stainless steels is suggested. In addition, an explanation is given for the anomalous effect of chromium in forming a y loop concurrent with the lowering of M, in iron-base alloys. It has been demonstrated that the effect of alloying elements on the Ms temperature is strongly dependent upon the influence of the alloying element on the thermodynamic properties of the y and a phases. Notwithstanding the fact that alloying elements affect the Ms temperature by changing the lattice parameters, elastic constants, and inter-facial energies of the a and y phases, their primary role is a thermodynamic one. Thermodynamic analyses have been presented for the iron-carbon&apos;-4 and iron-nickele systems in which equations are derived for Fa and FY, the free energies of the b.c.c. (or b.c.t.) and f.c.c. phases. These equations, which can be obtained with the aid of the equilibrium diagrams, can be used to help predict the Ms vs composition curves. This paper deals with a calculation of the thermodynamic properties necessary to compute AFffLY for iron-chromium alloys. In view of the lack of direct information concerning the activity of chromium in the a and y phases of iron, the regular solution approximationa,g was utilized to bridge the gap. After the necessary equations were derived for the iron-chromium system they were used to calculate AFff— Y for stainless steels by combining them with the previous results obtained for iron-nickel alloys. The results of these calculations offer a means of rationalizing the anomalous behavior of chromium in iron-base alloys. The latter depends on the regular solution approximation in contrast to the explanation offered by zener , which is based upon the "magnetic specific heat effect." THERMODYNAMICS OF THE IRON-CHROMIUM SYSTEM If y represents the atomic fraction of chromium in an iron-chromium alloy, then the free energy of the b.c.c. phase Fa, the f.c.c. phase FY, and the difference in free energy between the f.c.c. and b.c.c. phases of the same composition are given through [3] and Fmy represent the free energies of mixing of the a and y phases; while @era -&apos; and uFea 4Y represent the difference in free energy between f.c.c. and b.c.c. chromium and iron respectively. The values of AEFe0ff4Y in the temperature range between 0" and 900K ( .

Jan 1, 1960