Search Documents

By Alvaro Abreu, Thomas Fraser

The work described in this paper was carried out under the sponsorship of the Foreign Economics Administration and in cooperation with the Departamento Nacional da Produggo Mineral, Rio de Janeiro. The project was undertaken to obtain complete data on the variations in washability of coal to be used for coke manufacture in the steel industry and to determine the economy of preliminary hand-sorting operations. The coal-producing industry of Brazil is in that pioneering stage in which operating practices and methods are just being developed. Increased wartime demand for fuel, coincident with a drastic curtailment of foreign supplies due to lack of shipping facilities, has put a tremendous pressure on the national industry to furnish more coal. Under this incentive, production facilities are being -expanded- and new methods of operation are being tested. Such changes are being developed both by improvement of existing methods that originated in the field and by adaptation and modification of methods introduced from the United States and Europe. These mining conditions and mining practices in Brazil are typical of what the American mining engineer will find in many instances when he goes pioneering into the developing coal fields of the Southern Hemisphere. The producing coal fields of Brazil are all in the southern states of that country. The coal measures are in a band roughly paralleling the coast and extending in a generally southwesterly direction from northern Sao Paulo through the states of Paraná, Santa Catarina and Rio Grande do Sul to near the Uruguayan border in the vicinity of Bajé. The accompanying map1 (Fig. I) shows the general location of these fields and also the principal routes of movement of both national and imported coal in a late pre-war year (1940). Statistical data on production by states up to that year are given in Table I. Rio Grande do Sul is still the largest producer among the coal states; but wartime

Jan 1, 1947

By J. H. Swislzer

TWO-LIQUID miscibility gaps have been found to exist in both the CaO-SiO, system above 1705 and the Cr,03 system above 2200"c. Glasser and 0sborn3 studied the extension of these miscibility gaps into the Ca0-Si0,-Crz03 ternary system and reported that the two-liquid region is not present at temperatures below the monotectic temperature of 1705°C in the CaO-SiO, system. The present authors, in connection with other work on surface-tension measurements and foam stabilities in the same ternary system,4 observed that the miscibility gap exists at temperatures as low as 1600°C. A brief experimental study was devoted to deter- mining tie-line positions in the two-phase region. The technique used was to obtain a separation of phases at 1600°C, then to quench-in the high-temperature phases and obtain a chemical analysis of each phase. It was necessary to take special precautions in obtaining a phase separation because of a tendency toward emulsification of the two liquids. The procedure followed is described in the schematic drawing in Fig. 1. A small platinum crucible containing several pinholes on its sides was placed inside a larger platinum crucible. An excess of Crz03 was placed in the outer crucible, together with a prefused binary CaO-Si02 mixture, and the Cr203 was allowed to diffuse through the pinholes and saturate the same binary CaO-SiOl mixture in the smaller crucible. After equilibration at 1600°C, the inner crucible contained only the lighter liquid (liquid A) saturated with Cr203. The outer crucible contained layers of both liquids. Experimental data were obtained by analyzing the entire contents of the inner crucible and only the bottom layer of the larger crucible (liquid B). The upper layer of the outer crucible was not suitable for chemical-analysis purposes because dispersions of the second phase sometimes were found in the samples. The technique is described in more detail in Ref. 4. The same method was used by Grieveson and urkdoan' to study a miscibility gap in sulfate-ferrite melts, where the liquids were difficult to separate because of similarities in density. In addition to the phase-separation experiments, a few others were conducted to obtain information

Jan 1, 1964

By P. Gordon, A. S. Iyer

IN a paper on the mechanical behavior of heat-treated steel, N. H. Polakowski' put forward arguments to the effect that the stored energy resulting from the deformation of metals should be reduced during the inital stages of subsequent deformation carried out under conditions which produce work softening. At the time (1957) the only energy measurements available as indirect evidence on this point were the results of M. M. Degtyarev,2 some of which Polakowski reproduced in his Fig. 6, and which are again reproduced here in Fig. 1. The solid lines in the upper part of Fig. 1 are Degtyarev's, the dashed Lines Polakowski's prediction of the true trend of the stored energy in copper samples pre-strained in tension and then given various amounts of subsequent compression. The accuracy of this prediction has been borne out by some experiments carried out on American Smelting and Refining Co. copper (99.999' percent Cu) by the present authors. Bars of this copper about 0.4 in. in diam and 12 in. long were prepared by vacuum melting and casting, followed by cold forging and swaging in several stages of about 40 pct reduction in area with intermediate recrystallization anneals. After the final anneal one bar was deformed in tension to 30 pct elongation; the gage length was then cut into several samples which were given axial compressions of various amounts. The hardness of

Jan 1, 1960

By Lewis W. MacNaughton

The North Texas district, as herein defined, includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita, and Wil-barger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, are usually modified by stratigraphic changes in the sediments. Excepting the fields in southeastern Baylor, southern Archer, and southwestern Clay Counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsylvanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. Developments during 1940 The encouraging outcome of exploration and development in Montague and Cooke Counties and generally greater activity throughout the district resulted in the drilling of some 1700 wells during 1940, about 350 more wells than were drilled in 1939. Approximately 1250 of these tests were completed as oil wells. Production likewise increased during I940 to the extent of 8 million barrels more than the 25 1/2 million barrels produced in 1939. In spite of this large increase in production, known oil reserves again increased substantially. As is usually characteristic of this district, the new reserves were from a large number of fields, none of which were of such magnitude as to be important to the oil industry. Nevertheless, the Fargo field, Wilbarger County, deserves mention as one of the more important discoveries in this district during 1940. Following seismic surveys, the hmerada Petroleum Corporation located its No. I Goodpasture in sec. 35, block IS, H. and T. C. R. R. Co. survey, and drilled it to a total depth of 6717 ft. This well was completed in July 1940 through perforations in the casing from a pay between 3230 and 3252 ft. for an initial production of 241.5 bbl. on an 8-hr. pumping test. Other potential producing horizons were found in the Pennsyl-vanian at depths of 3960 to 3995 ft., 4208 to 11.234 ft., 4407 to 4422 ft., and in the Ordovician at 6300 ft. Wells completed to date in the several Pennsylvanian horizons have an average daily potential of 600 bbl. of oil. Although no wells have yet been completed in the Ellenburger dolomite (Ordovician), the discovery well swabbed I5 bbl. per hour from this formation before plugging back for completion in an upper horizon.

Jan 1, 1941

By Lewis W. MacNaughton

The North Texas district, as herein defined, includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita, and Wil-barger. This area covers generally the crest and south flank of a system of buried mountains known as the Red River uplift. The oil and gas accumulations along this feature are in traps, which, although localized by structures incident to the regional uplift, are usually modified by stratigraphic changes in the sediments. Excepting the fields in southeastern Baylor, southern Archer, and southwestern Clay Counties, all the fields within the district are on this Red River uplift. These exceptions, which have the same type of oil and gas accumulation as the other fields, are on the extreme north end of the Bend arch, which is a broad anticline plunging northward from the Llano uplift in central Texas to Archer County. The larger part of past oil and gas production has come from Pennsylvanian strata, with less important amounts from the Permian, and minor but increasingly important quantities from the Ordovician. Developments during 1940 The encouraging outcome of exploration and development in Montague and Cooke Counties and generally greater activity throughout the district resulted in the drilling of some 1700 wells during 1940, about 350 more wells than were drilled in 1939. Approximately 1250 of these tests were completed as oil wells. Production likewise increased during I940 to the extent of 8 million barrels more than the 25 1/2 million barrels produced in 1939. In spite of this large increase in production, known oil reserves again increased substantially. As is usually characteristic of this district, the new reserves were from a large number of fields, none of which were of such magnitude as to be important to the oil industry. Nevertheless, the Fargo field, Wilbarger County, deserves mention as one of the more important discoveries in this district during 1940. Following seismic surveys, the hmerada Petroleum Corporation located its No. I Goodpasture in sec. 35, block IS, H. and T. C. R. R. Co. survey, and drilled it to a total depth of 6717 ft. This well was completed in July 1940 through perforations in the casing from a pay between 3230 and 3252 ft. for an initial production of 241.5 bbl. on an 8-hr. pumping test. Other potential producing horizons were found in the Pennsyl-vanian at depths of 3960 to 3995 ft., 4208 to 11.234 ft., 4407 to 4422 ft., and in the Ordovician at 6300 ft. Wells completed to date in the several Pennsylvanian horizons have an average daily potential of 600 bbl. of oil. Although no wells have yet been completed in the Ellenburger dolomite (Ordovician), the discovery well swabbed I5 bbl. per hour from this formation before plugging back for completion in an upper horizon.

Jan 1, 1941

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By F. M. Lewis, E. C. Johnson

Used as a classifier in a plant expanding capacity or changing to closed-circuit operation, the liquid-solid cyclone offers the advantage of being adaptable to existing conditions. This paper presents the costs involved and experience gained from operating a unit of this kind. BY now application of the liquid-solid cyclone to various classification problems in the chemical and metallurgical fields is more or less familiar. A less publicized application receiving wider consideration as time goes on is its use as a classifier in closed-circuit grinding operations. This paper presents the costs involved and the experience gained from operating a unit of this kind. In May 1951 the Tennessee Copper Co. installed in its London mill at Copperhill, Tenn., a liquid-solid cyclone in closed circuit with a 6x12-ft ball mill. The circuit in which this cyclone is used is the regrind or secondary grinding circuit of a copper flotation plant. Originally it consisted of a 7x1-ft conical ball mill in closed circuit with a bowl classifier. Changes made in the primary grinding circuit of the mill necessitated a regrind circuit of greater capacity. The bulk concentrate to be ground was raised from 900 or 1000 tpd to 1200 or 1300 tpd, and to accommodate this increase a 6x12-ft ball mill which had been in the primary grinding circuit was moved into the regrind circuit. When this was done it was found that the classifier was too small to give efficient operation. Space in the plant was at a premium, and since use of the cyclone offered considerable economy the installation shown in Figs. 1-3 was made. The unit installed is a 24-in. diam cyclone classifier with a 20" cone angle. Diameter of the vortex finder is 8 in., the feed entrance area 20 sq. in. Maximum diameter of the adjustable apex valve is 6 in. and minimum diameter approximately 3.5 in. To refer again to Figs. 1 and 2, the cyclone* is mounted motor. It is charged with 18 tons of 1-in. balls. The overflow, or fines, passes by gravity directly to the copper flotation plant. The ball mill discharge and the new feed combine in a sump from which they are sent to the cone by an 8x6 SRL pump at a rate of 497 gpm. Pressure at the cyclone is 5 psi. For reasons dictated by the nature of the ore treated, particularly the bonding of fine grains of chalcopyrite to pyrrhotite, the froth from the second cell of the copper rougher circuit is returned to the regrind mill. This flow, which somewhat complicates the standard closed-circuit calculation, is seen in Fig. 1 to be 156 tpd of solids. This combines with the cyclone classifier underflow to constitute the ball mill feed. The requirement of the regrind product is that it be 77 to 80 pct —200 mesh. The liquid-solids cyclone operating in conjunction with the 6x12-ft mill adequately met this requirement. Of primary importance is the fact that this arrangement provided sufficient classification capacity to replace the undersized classifier and was capable of building up a circulating load to 87 pct, large enough to give an efficient grind. In this instance the circulating load is taken as the ratio of sands to new feed. Any comparison of performance between this liquid-solid cyclone and the replaced classifier would of course be unfair, since the bowl classifier was

Jan 1, 1955

By J. Brett, S. Friedman

A study of the diffusion of nickel into both fibrous and recrystallized 0.065-in.-diam silica-alumina doped tungsten wire at 1200°C has been conducted. The diffusion profiles were determined by chemical dissolulion of successive circumferential layers and spectro-photometric determination of nickel in the etchant. It was shown that the diffusion of nickel into tungsten is markedly structure-sensitive. No significant amount of nickel could be introduced at 1200°C into tungsten which had first been recrystallized at temperatures of 2300°C, leading to an upper limit estimate for the bulk diffusivity of nickel in tungsten of 10-11 sq cm per sec at 1200°C. However, nickel did diffuse into initially fibrous wires, caused re crystallization, and was alsays present at the advancing recrystallization front. The accumulation of nickel in an initially fibrous region ceases when the recrystallization front arrives. The characteristics of the resulting diffusion profiles are explained in terms of the relation between diffusion processes and micro structural changes. WHILE it is well-known that the presence of nickel and certain other metals causes low-temperature recrystallization of the cold-worked fibrous structure of doped tungsten,''' the character of the phenomenon is not well understood. Recently it was shown that the recrystallization reaction can be induced at low temperatures by the presence of solid nickel on the surface of doped wire, but not by exposure to nickel vapors.3 Once recrystallization was initiated, a continued source of nickel was required for propagation of the recrystallization front. The phenomenon appeared to be a complicated solid-state reaction since, in addition to the change in structure of the tungsten from fibrous to equiaxed grains, diffusion of nickel from the surface into the recrystallized and fibrous structures was occurring with possible chemical reaction between nickel and tungsten at the surface and interaction of nickel with the dopants which ordinarily stabilize the fibrous structure within the wire. The objective of the present work was to study the diffusion of nickel into fibrous and recrystallized tungsten structures in order to clarify the relationship of the diffusion process to nickel-induced recrystallization. Studies of interdiffusion in the Ni-W system4"7 have been principally concerned with the mobility of tungsten in nickel. Information on diffusion of nickel in tungsten is meager, and there seem to be no studies of the mobility of nickel in tungsten which elucidate the structural aspects of the phenomenon. The present experiments were designed to determine the diffusivity of nickel at 1200°C in fibrous tungsten, in large-grained tungsten prerecrystallized at high tem- perature, and in tungsten recrystallized at 1200°C due to the presence of nickel. Although the concentration profiles were determined in these experiments, unexpected changes in boundary conditions or complex diffusion paths complicated the analysis of these profiles so that the interpretation could not be readily expressed in terms of simple diffusivities. EXPERIMENTAL PROCEDURE The experiments were conducted on Sylvania 0.065-in.-diam silica-alumina doped commercial tungsten wire, hereafter designated as ordinary doped wire. A special lot of 0.065-in.-diam silica-alumina doped low-nickel wire was also used. Impurity analyses of the wire are given in Table I. The experimental design is shown in Fig. 1. All heat treatments were conducted in vacuum. Two groups of ordinary doped wire were prepared for diffusion with nickel. One group in the as-received (fibrous) condition was elec-tropolished, nickel-plated, and annealed at 1200°C for 20 and 40 hr, or was exposed to nickel vapor at 1200°C for 20 and 40 hr. The second group was recrystallized to an equiaxed grain structure at 2300°C for 3 hr, electropolished, nickel-plated, or exposed to nickel vapor for anneals at 1200°C for 20 and 40 hr.

Jan 1, 1969

By M. Duclos, A. Sawatzky

A simple model has been developed which describes the steady-state solute distribution in Ti-H type systems above the eutectoid temperature in the presence of a temperature gradient. The solute distribution is dependent on the shape of the phase boundaries. An interesting result, and one that is not observed at steady state in thermal diffusion below the eutectoid temperature, is the existence of a two-phase region. The heat of transport for hydrogen in a titanium, Q*a, over the temperature range 275" to 650.C is determined to be 4500 * 230 cal per mole. The heat of transport for hydrogen in B titanium, QB* over the temperature range 320" to 590.C is found to be 630 ± 200 cal per mole. It is also shown that thermal diffusion provides a method by which phase bounduries above the eutectoid may be determined in Ti-H type systems. IN modern technology materials are being used at constantly increasing temperatures under greater temperature gradients. Thus atomic migration in metal alloys due to a temperature gradient (thermal diffusion) may in some cases occur to an observable extent. The thermal diffusion of hydrogen in zirconium has in recent years received considerable attention1-' because of the use of zirconium alloys in nuclear power reactors. The thermal diffusion kinetics below the eutectoid (547°C) are fairly well understood. At steady state the solid solution, a, and hydride, 6, phases are completely separated with the hydride precipitating at the lower temperatures. No experimental work has been carried out in the a + B region although Droege4 suggested that a complete separation of the two phases, as observed at temperatures below the eutectoid, might not always occur. In the present investigation a simple model has been used to determine the steady-state solute distribution under a temperature gradient in Zr-H type systems heated above the eutectoid temperature. The solute distribution is shown to be dependent on the shape of the phase boundaries in the constitutional diagrams and several typical cases are discussed. The model has been applied to Ti-H. This system was chosen in preference to Zr-H because of its much lower eutectoid temperature (-300°C as compared with 547.C), thereby reducing experimental errors due to oxidation and hydriding. The heats of transport for hydrogen in the a and B phases of titanium also have been determined since they were required to compare the proposed thermal diffusion model with experiment. THEORY In the presence of a temperature gradient the atomic flux in a single-phase region of a two-com-ponent system of which the atoms of only one component are diffusing is given by:' J = - U\dx + RT3 dx) which can be written as: j-D(dn/dt +Q*n/RT2)dt/dx [11 J - -D\dT + RT2)dx [1] where D = diffusion coefficient, n = solute concentration, T = absolute temperature, R = gas constant, dT/dx = temperature gradient, and Q* = heat of transport. At steady state (J = 0) Eq. [I] leads to the solute distribution: n = noexp Q*/RT where no = a constant depending on total solute content. The heat of transport Q* can be experimentally determined from the steady-state distribution. In the present paper we shall determine the solute distribution in systems having the constitutional diagram exemplified by Ti-H shown in Fig. l.' As shown, N,(T) and NB(T) are the equilibrium solute concentrations in the a and 0 phases at temperature T. Lines AA' and CC' define the region of interest to us. The following assumptions are made: 1) Steady-state conditions prevail. 2) In a single-phase region all points on an isotherm have the same thermodynamic potential so that the composition over an isotherm is uniform. If a two-phase region exists, thermodynamic equilibrium is found only at phase interfaces. However, we assume the component of the concentration gradient along an isotherm to be small so that the composition in each phase is approximately the same as at the interface and is given by the constitutional diagram, Fig. 1. 3) There is appreciable diffusion of only one component. 4) We shall consider only the case where Qa*, QB*, and Qg*, the heats of transport for solute diffusion in the a, B, and 6 phases, respectively, are positive. This has been observed for the thermal diffusion of hydrogen in zirconium3 and titanium.10 We will show that the steady-state solute distribution above the eutectoid is primarily determined by the heats of transport and the temperature dependence of Na(T) and Np(T). It may be quite different from the steady-state distribution below the eutectoid. For example, we will see that, under certain conditions,

Jan 1, 1970

By D. J. Carney, J. Chipman, N. J. Grant

G. A. Moore—The tin-fusion method has been a very favorable possibility for many years. The authors apparently have settled the question that delayed the method for a long time by showing that no hydrogen is absorbed in the tin. This, of course, is very important. I want to make a few remarks concerning the absolute accuracy of analysis, which must be the final basis for deciding among the various methods. From the figures in the paper, there seems to be some remaining slight discrepancy on the actual amount of hydrogen present in various samples which may be presumed essentially identical. (This is of the order of the precision of individual analyses but appears in averaged results.) From the analyst's viewpoint, the tally of hydrogen content can be regarded as occurring in three portions. First is a large portion which comes off easily and automatically during sample storage and later on heating in the apparatus. This is fairly easily analyzed. Second is an item which may be either positive or negative in the tally sheet. In warm or hot evolution, this is a portion which, in practice, can never be re-

Jan 1, 1951

By Ernest Kirkendall

The amount of research done in the last fen years on the subject of diffusion in solid metals is significant of the importance of this problem. To review the literature dealing with diffusion is unnecessary here. Deschl in 1912 reviewed the work that had been done on diffusion in solids and gave a bibliography of the literature published before that time. Mehl's paper in 19362 is an excellent review of diffusion in metals and contains a large bibliography. Of importance also for it? review and bibliography is an article by 14. I. Krynitsky.~ While considerable material lias appeared in the literature on diffusion in brass, the amount of information is not great compared to that pertaining to some of the other alloys. Most of the information published is of a qualitative nature; that which is quantitative varies considerably. Thus the quantitative determination of the rates of diffusion of copper and zinc in alpha brass by a new method appeared worth while. In the present investigation the rate of diffusion of zinc in approximately the same composition alpha brass has been determined :it three temperatures. Procedure The method used consisted of plating copper on a beta brass, heating it, to allow diffusion to take place, and measuring the concentration of copper by determining the lattice constant of the alloy. This method is unique in that it uses a beta brass of such a composition that at the tem perature at which diffusion takes place the beta brass is saturated wit11 copper. Thus, while the beta brass supplies thc zinc, no diffusion takes

Jan 1, 1939

By Ernest Kirkendall

The amount of research done in the last fen years on the subject of diffusion in solid metals is significant of the importance of this problem. To review the literature dealing with diffusion is unnecessary here. Deschl in 1912 reviewed the work that had been done on diffusion in solids and gave a bibliography of the literature published before that time. Mehl's paper in 19362 is an excellent review of diffusion in metals and contains a large bibliography. Of importance also for it? review and bibliography is an article by 14. I. Krynitsky.~ While considerable material lias appeared in the literature on diffusion in brass, the amount of information is not great compared to that pertaining to some of the other alloys. Most of the information published is of a qualitative nature; that which is quantitative varies considerably. Thus the quantitative determination of the rates of diffusion of copper and zinc in alpha brass by a new method appeared worth while. In the present investigation the rate of diffusion of zinc in approximately the same composition alpha brass has been determined :it three temperatures. Procedure The method used consisted of plating copper on a beta brass, heating it, to allow diffusion to take place, and measuring the concentration of copper by determining the lattice constant of the alloy. This method is unique in that it uses a beta brass of such a composition that at the tem perature at which diffusion takes place the beta brass is saturated wit11 copper. Thus, while the beta brass supplies thc zinc, no diffusion takes

Jan 1, 1939

By T. L. McCall

THE late Walter Herd1 in 1929 gave a full description of past and present conditions in No. 2 mine, Springhill, Nova Scotia, developed theories regarding the cause of these bumps and made certain suggestions regarding possible methods of future development. Recapitulating briefly from Mr. Herd's paper, the seam is bituminous coal, averages 9 ft. in thickness and has a well defined parting containing fusain about 14 in. from the roof. This roof coal is somewhat stronger than the rest of the seam and has a tendency to cling to the roof. The pitch of the seam where it is now being worked is about 20°. The first manifestations of bumps began when the room and pillar workings had reached a depth of cover of 1900 ft. and under continuously increasing depth of cover these bumps increased to such an extent, both in number and severity, that in the year 1924 it became apparent that some change in the system of extraction was necessary. After closely studying all the factors involved and benefiting largely by valuable out-side advice obtained by the Provincial Department of Mines of Nova Scotia,2 the system of working was changed from room and pillar to longwall retreating. Mr. Herd's paper described in detail three remarkable bumps in the year 1928 in April, July and October that affected the 5700-ft. and 5900-ft. East levels, the last bump being so severe both in intensity and in extent of damage done that this district was abandoned. The longwall workings to the west of the slope had been stopped in the year 1926 owing to an inbreak of water, coming from the flooded waste of No. 3 seam lying some 400 ft. vertically overhead. This inflow was not excessive, but a large quantity of water being impounded in the old workings it was considered advisable to take the prudent course and not incur the risk of possibly increasing the flow by further working. This district has remained idle ever since.

Jan 1, 1934

By R. Maddin, W. R. Hibbard

A series of X ray experiments conducted by G. I. Taylor' in 1927 and later substantiated in 1939 by J. A. Collins2 both on axially strained aluminum single crystals, revealed evidence that during single slip crystallite rotation occurs in such a manner that " all parts of the material rotated about the transverse direction in the plane of slip."l The actual method of preparing the specimens for X ray examination is not discussed in detail by Taylor except to say that "this specimen was cut parallel to the plane of slip, as calculated from measurements of marks in the surface of the specimen. It was ground and etched till the effect of the new cuts had disappeared. This was verified by applying the same treatment to an un-distorted specimen. The X ray reflectionsl in this case were perfect ones."' Collins, on the other hand, cut his crystals in a mechanical shaper. These surfaces were polished on No. 1, No. 1/0, No. 2/0 and No. 3/0 papers and on a broadcloth lap using No. 600 alundum as a polishing medium. "Finally, the surface was deeply etched in Tucker's reagent. An unde-formed crystal was prepared in the manner described and X rayed to determine whether or not the machining and polishing operations had produced any strain or distortion in the crystal. The Laue spots all seem to be sharp, free from tails and streaks indicating no detectable strains had been introduced in the crystals." Taylor's X ray technique involved the use of "homogeneous X rays from an iron anti-cathode"; whereas Collins used Ka radiation of copper at 31kv and 20 milliamperes. Glancing angle X ray photograms were taken (1) with the axis of rotation of the spectrometer table in the plane of slip and at right angles to the slip direction, and (2) with the axis of the spectrometer table lying along the slip direction. However, eight minute exposures were used in each case and the angle setting of the spectrometer table was increased by one degree for each exposure. With the discovery of the action of three slip systems3 in the plastic deformation of single crystalline alpha brass where, formerly, only one had

Jan 1, 1950

By Persifor Frazer

The mines which I am about to describe are all situated in the northern part of the States of Nuevo Leon and Coahuila, Mexico, between the twenty-sixth and twenty-seventh degrees of latitude. They might be grouped, orographically, into four classes: 1. Those in the Sierra de la Ygnana chain; 2. Those in the Sierra de Gomez chain; 3. Those in the Cerro Mercado; 4. Those in the Sierra de San Marcos chain. (See large map.) The first two of these may be further arranged in one geographical district, to which the name, "the Villaldatna. district," may be applied, and the last may be ascribed to the geographical district of " Monclova." Geologically described, the country rock, in which four of the six mines occnr, is a limestone, concerning which a few words will be said further on, to wit.: The Arroyo (gulch), the Montanos and the Pinitos (pines), in the Villaldama district, and La Paloma (the dove), or Iron Mine, in the Monclova district. The San Rafael appears to lie in granite, or a heavy-bedded gneiss, presenting most of the characteristics of the latter, though the contact plane of the limestone is not far off. It is certainly worthy of attention that the ore occurs in that portion of the crystalline rock, which is nearest to the limestone, and it has been thought by some observers to be a true contact vein. It is well known that veins of this character are very often distinguished for constancy and richness. Although the undersigned cannot entirely free himself from the impression that this proximity of different formations has had an important influence in the origin of the part of the vein on which this mine is situated; still he was unable to establish it actually at the contact of the limestone and granite, but rather a short distance within the latter. Two openings of the Riojas vein were respectively in limestone and in rotten whitish granite, but this fact, if established (as by the correspondence of the strike line of the vein in direction with that of a line joining the

Jan 1, 1884

By B. Chalmers, S. Wojciechowski

THE structure of the equiaxed zone of several A1-Cu samples mechanically stirred during unidirectional solidification was examined. The stirring was produced by rotary oscillation of the mold about its vertical axis.' It was found that in Some samples the structure is not of the same type over the whole of the equiaxed zone; it consists of regions with two different etching responses. Fig. 1 shows this structure in a Al-1 wt pct ku sample. The lighter etching regions with a coarse structure form something like a network and the darker etching regions with a finer structure can be observed as the continuation of the coarse structure inside this network. The difference in size and shape of the dendrite branches (they are rounded in the coarser structure) is similar to that found by Williamson and Chalmers in ice crystals solidified in undercooled water: when the amount of undercooling was small, the ice crystals were more rounded and coarser than these solidified with a larger amount of undercooling.' It seems justified to conclude that the observed structure resulted from solidification under different thermal conditions: the coarser structure solidified first out of the "purer" liquid and with a smaller amount of undercooling and the finer was formed later out of solute-enriched liquid under conditions of much more rapid heat extraction. A considerable change in the heat flow conditions at the later stages of solidification can be easily understood by taking into account that the coarser crystals form a continuous network and the amount of trapped liquid is relatively small; hence the contribution of latent heat is much smaller in the later stages of solidification. The difference in structure and etching characteristic reflects a difference in composition between these two regions. It was found that the darker etching re- gions are harder (30.4 to 31.3 HV5) than the lighter etching ones (25 to 26 HV5). A similar type of structure was found in a A1-4 wt pct Cu sample grown by Czochralski method. Fig. 2 shows the structure in the lower part of a sample grown slowly and then decanted by a rapid removing of the sample from the melt. In a few places trapped liquid solidified in the same manner as in the sample shown in Fig. 1.

Jan 1, 1968

By P. W. Neurath, R. E. Waite

INFORMATION is available on the effect of stress on permeability, coercive force, and hysteresis for a variety of materials' but for the technically important grain-oriented 3 pct Si-Fe' the stress effects are not adequately covered in the literature; in addition, most of the stress data do not permit estimation of what would happen to the 60 cycle watt losses of the material under stress. Direct measurement of these effects therefore has been made and appears to be of considerable theoretical as well as practical interest. Losses were measured on the central 25 cm portion of 40~3~0.035 cm samples which could be stressed in a small tensile machine built for this purpose. Under tension the following effects, illustrated in the figures by a particular example, were observed: 1—"Unstrained" material of commercially acceptable loss level shows no change or a small increase in loss at low elastic stresses. For the sample shown in the figures, this is illustrated during the initial run, where a 7 pct increase is observed (Fig. 1). 2—There is no additional change in loss when the sample is further strained up to the elastic limit (Fig. 1). Within that limit the loss-stress curve is reversible. This is not illustrated in Fig. 1. 3—Even in the plastic range only small increases in loss are observed as long as the sample is kept under stress (Fig. 2, point N); often no increase can be observed (Fig. 1). 4—A large increase in watt losses is observed after removal of the stress subsequent to plastic deformation (Figs. 1 and 2). 5—All, or nearly all, of the foregoing increase in loss due to plastic deformation can be eliminated by a reapplication of tensile stress but returns upon removal of this stress. This is illustrated in the third run (Fig. 3). This run remains within the elastic limit and shows the reversibility of the stress-loss curve under this condition. These findings have been confirmed on large Samples (approximately 200~10~0.035 cm and larger) except that under 1 no initial increase in loss was ever observed on these. The accuracy of the watt loss measurements is of the order of 1 pct. Neither bending of the sample in the tensioning device nor a redistribution of flux along the width of the sample accounts for these results. They therefore must be explained on the basis of either a change in the domain configuration due to stress or a change in the domain wall mobility. Acknowledgment The assistance of Mr. Robert L. TenBroeck with the instrumentation is gratefully acknowledged.

Jan 1, 1956

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

INTRODUCTION THE reaction of carbon in solid solution in a metal with the surface oxide film on many metals may be inferred from thermodynamic calculations for high vacua and high temperature conditions. Holm1 has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. Considerable work has been described in the literature on the decarburization reaction. Several general references may be noted.2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides 0n strips of various types of chrome-nickel alloys. Some of the early experiments on the behavior of 13 pct chrome-iron in vacua of the order of 5 X 106 mm and at a temperature of 600°C have been reported.5 These experiments showed a slow reaction with the residual oxygen or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600°C pure enough to reduce Cr203 formed on the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome iron and Nichrome V has been investigated in the thin film range by Gulbransen, Phelps and Hickman,6 and shown to be Cr203. It was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pct nickel and 20 pct chromium was heated to 850°C in a high vacuum, the specimen' lost weight. The rate of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. TYPE REACTIONS Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature, of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type. They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: [I. Metal • (gas) ;--* metal + gas - degassing of the metal 2. xM(s) + y ½ 02(g) tom- M.0„ (s) – oxidation]

Jan 1, 1948

By T. M. Geffen, R. E. Gladfelter

Lipson1 has recently presented a technical note wherein theoretical considerations were used to demonstrate. that the adsorption us saturation relation for a linear absorption method is not necessarily a single valued function of saturation.1 It was concluded that the absorption us saturation relationship is subject to the same hysteretic effect as is the flow behavior between the drainage and imbibition systems. It is the purpose of this note to show, by experimental results, that for the manner in which fluids are distributed in porous materials during fluid flow, the relative X-ray absorption us saturation relationship is single-valued regardless of the saturation history. The design of the apparatus used to measure relative X-ray absorption of cores undergoing fluid flow tests is similar to that described by Morgan, McDowell and Doty. A few modifications have been incorporated in the design to increase sensitivity and simplicity of measurement. The sensitivity is such that for usual types of cores a recording pen movement of approximately 12 linear in. is occasioned between the recording of the core dry and when it is completely full of an absorbing liquid, a solution of approximately five per cent by volume of iodo-benzene in a close-cut hydrocarbon fraction, or a solution of 50,000 ppm sodium iodide in water. Two types of experiments were conducted, one in which the liquid was inside the core, and the other with the liquid outside the core. Tests with the liquid inside the core were run to cover the saturation range encountered in both the drainage (gas drive) and imbibition (liquid flood) flow systems. It is pointed out that the same core was used, but the tests were conducted at different times with the recording mechanism balanced at a different position. Therefore, the absolute values of relative X-ray intensity at any saturation are not the same in each test. In the second type of test the same core was used, but this time its pore space cmtained only gas, and various thicknesses of oil contained in plastic cells were placed in front of the dry core. As before. the relative X-ray ah- sorption was measured and compared to the quantity of oil in front of the core. The arrangement of the fluids with respect to the path of X-rays in these two types of tests represent fluid distributions of a wider difference than can be expected between that established in a core just due to imbibition and drainage saturation flow histories. Thus any deviation from a straight line relationship of the log of the relative X-ray intensity us saturation calibration should be readily apparent. Results of the laboratory tests are given in Fig. 1. A schematic diagram showing the position of the fluids with respect to the path of the X-ray beam is given for the two cases investigated. In the case where the oil existed outside the core (Case B), the log of the X-ray intensity (log, I/I,) is related directly to the cell thickness (amount of oil in X-ray beam path). This correlation is in full agreement with X-ray theory. In the case where the oil or water existed inside the core (Case A) which covers both drainage and imbibition types of flow processes, again the relationship between absorption and saturation (amount of oil in X-ray beam path

Jan 1, 1952