Search Documents

Jan 1, 1940

Jan 1, 1944

Jan 1, 1930

Jan 1, 1937

Jan 1, 1943

Jan 1, 1944

Jan 1, 1942

Jan 1, 1943

By F. E. Pawlek, J. K. Gerlach

The chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. In the first part of the investigations the reaction rate of the chlorides of sodium or calcium with gas mixtures of SO,-0, or SO ,-O2 ,-SO , was measured. The rate for reactions with gas mixtures SO2-O2 is ThE chloridizing roasting of ores is applied when metal sulfides and oxides are to be converted into soluble or volatile compounds. At present the process is mainly applied to produce nonferrous metals which occur in pyrite cinders in small concentrations. Thereby the nonferrous metals are converted into water-soluble, acid-soluble, or volatile compounds whereas all the iron remains as insoluble oxide. The chlorine required is either obtained from the admixed chlorides of sodium or calcium or added in the gaseous state. The reactions occurring during the roasting process can be divided into two groups: solid-solid reaction and gas-solid reaction. The reactions between solids proceed by means of solid-state diffusion and are therefore of low velocity. The heterogeneous reactions between solids and gases of the roasting atmosphere5 are high-velocity processes and determine the velocity of the chloridizing roasting. These gas-solid reactions shall be the subject of the paper presented. In order to investigate the still little-known processes which occur during the chloridizing roasting 6-' the complex reaction is split into several partial steps. First the reactions of NaCl and CaCl, with gas mixtures of SO2 and 0, have been investigated at temperatures between 500" and 600°C by measuring the weight increase of the samples. The gas mixtures used in this series of experiments had first variable compositions, then the amount of SO 2 had been increased. Furthermore the influence of Fe 2 O3 admixtures upon these reactions, the behavior of pure Fe 2 O3 with the gaseous reactants, and the chlorination of the sulfides of lead, copper, nickel, and zinc have been investigated. FORMATION OF GASEOUS CHLORINE Pyrite cinders are never completely roasted and therefore contain still a small amount of sulfide sulfur. When heated again in air, this sulfur is converted into SO,. Accordingly the formation of chlorine can first be described by the reactions: dependent on the composition of the gas phase. If more than 1 pct SO 3 is added to the roasting gas, the reaction rate is determined only by the concentrations of the SO,. In the second part the reactions between chlorine and metal sulfides are discussed. The rate of formation of gaseous chlorine is higher by me order of magnitude than is the reaction rate between ZnS and chlorine. The reaction rate of NiS and PbS lies considerably below that of ZnS. The conversion rate of both pure Fe 2 O 3 and Fe 2 O 3 containing NaCl or CaCl2 when reacting with SO2-O2, mixtures with and without SO3 portions was measured at temperatures of 500", 550°, and 600°C. The weight increase of pressings was determined by means of a spiral balanceg and the reaction rate calculated therefrom according to Eqs. [ll to [31 and [5] to [7]. The prepared samples were suspended on a platinum filament in a vertically mounted tube of mullite (ID 4 cm, length 110 cm) which could be heated by a resistance tube furnace. The platinum filament was tied to the lower end of the spiral balance. A supremax glass tube (length 70 cm) was mounted gas-tight on top of the reaction tube. The unit was sealed up at its top by a ground-in stopper which was holding the spiral balance with the sample. The spiral balance therefore hung outside the high-temperature region of the furnace. Fig. 2 shows the experimental arrangement schematically. While lowering the sample into the reaction tube pure nitrogen was flowing through the reaction zone providing a protective atmosphere. After the sample had reached the reaction temperature within approximately 1 min, the protective gas was replaced by the sulfur dioxide-oxygen reaction mixture. It took about 30 sec until the mixture filled the tube homogeneously. A Ni/NiCr thermocouple placed in the center of the furnace where the sample hung during the measure-

Jan 1, 1968

By R. G. Aspden

Crystals with an (001) [loo] initial orientation of an iron-base alloy containing 3 pct Si were cold rolled with and without the use of constraints. A major difference in the rolling and annealing textures was observed between crystals rolled with and without constraints. These data show that the contribution of constraints at grain boundaries in a poly crystalline sheet should be considered in applying textural data on single crystals to grains in an aggregate. SILICON-iron alloys with a cube texture have been recently developed and their magnetic characteristics reported.1-4 Of interest in the development of this texture were the textural changes of single crystals accompanying rolling and annealing and the influence of constraints at grain boundaries in an aggregate on the behavior of individual grains. The present study was primarily concerned with the effect of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001)[100]. Barrett and Levenson5 were among the first to observe an influence of constraints at grain boundaries on the textural changes of individual grains during deformation. They tested Taylor's6 theory of plastic deformation of face-centered-cubic metals in which deformation textures were predicted. About one-third of the grains in poly crystalline aluminum did not rotate as predicted. Grains of the same initial orientation were observed to rotate in different directions under the influence of applied stress and anisotropic flow of neighboring grains. Recently, the various inhomogeneities of flow of crystals in an aggregate have been studied7'8 and reviewed.9-11 Barrett and Levenson" rolled (001) [loo] iron single crystals inserted in close-fitting holes in copper to limit lateral flow and to simulate rolling of grains in an aggregate. Deformation bands were formed after a 90 pct reduction in thickness, and the cold-rolling texture contained two components described by rotating the (001)[100] about 35 deg in both directions around the normal of the rolling plane. No annealing textures were reported. Chen and Maddin13 rolled molybdenum single crystals initially (001) [loo]. The crystals were mounted between two hardened silicon-iron plates and 96 pct reduced in thickness by rolling at a low rate of reduction, about 0.0001 in. per pass. The deformation texture had the mean orientation of (001) [loo], and the azimuthal spread included orientations described by rotating (001) [loo] about 35 deg in both directions about the pole of the rolling plane. The presence of deformation bands were not reported by Chen and Maddin or detected in subsequent work of Ujiiye and Maddin.14 The ideal orientation of the annealing texture was (001) [loo]. Recently, Walter and Hibbard 15 reported on the textures of 3 pct Si-Fe alloy crystals initially near (001) [loo]. Each crystal was in an aggregate cut from a columnar ingot. After 66 pct reduction by rolling, the texture consisted of two symmetrical components which had the orientations described by rotating (001) [loo] about 30 deg in both directions about the pole of the rolling plane. Annealing texture was near (001) [loo]. In the above work, the textures of body-centered-cubic crystals were studied after rolling under the influence of constraints. The deformation textures varied from (001) [loo] to near the (001) [110] type and appeared sensitive to the manner in which the crystals were rolled. No textural data were available on the effect of rolling (001) [loo] crystals with and without constraints. The purpose of the present work was to evaluate the influence of constraints during rolling on the textures of 3 pct Si-Fe crystals initially (001) [loo]. Rolling and annealing textures were studied for a) crystals rolled with no constraints at different rates of reduction, and b) crystals rolled with constraints imposed by neighboring grains and by plates between which a crystal was "sandwiched". PROCEDURES AND EXPERIMENTAL TECHNIQUES Data are presented on four crystals which are representative of several crystals studied. The orientation of each crystal prior to rolling was (001) [loo] as determined by the Laue X-ray back-reflection method," i.e., each crystal had an (001) within 3 deg of the rolling plane and [100] within 3 deg of the rolling direction. These crystals were obtained from two iron-base alloys containing 3 pct Si by weight which were prepared by vacuum melting electrolytic iron and a commercial grade of silicon. Crystals 1, 2, and S-1 were cut from a large single crystal grown from the melt of one alloy by the Bridgman technique17 in an apparatus described by

Jan 1, 1960

By H. C. Rogers

A phenomenological study of the failure of polycry stalline ductile metals at room temperature was carried out using light and electron microscopy. Tensile fractures as well as sections of partially fractured bars of OFHC copper in particular were examined. The initiation and growth of the central crack in the neck of a tensile specimen occurs by void formation. After the formation of the central crack the f'racture may be completed in either of two ways: by further void formation or by an "allernating slip" mechanism. The first leads to a "cup-cone" failure; the second, to a "double-cup" failure. In the past decade or decade and a half there has been a great deal of emphasis on the solution of the problem of the brittle fracture of metals, particularly those which normally exhibit considerable ductility such as steel. Since the problem of the fracture of metals after large plastic strains has less immediate commercial or defense significance, there has been considerably less effort expended in describing the details of the phenomenology and determining the mechanism of this type of fracture. The present research was undertaken to increase our knowledge in this area. The problem of ductile fracture has not been neglected completely, however. Ludwik1 first found by sectioning a necked but unbroken tensile specimen of aluminum that fracture began with a large internal crack which appeared to have started in the center of the neck. Examination of the fracture indicated that the crack had propagated radially with increasing deformation until a point was reached at which the path of the fracture suddenly left this transverse plane and proceeded at approximately 45 deg to the stress axis until the surface was reached. This gives rise to the commonly observed cup-cone tensile fracture. When MacGregor2 was attempting to demonstrate the linearity of the true stress-true strain curve from necking until fracture, he found that copper was anomalous in that the stress dropped off markedly from the straight line value before fracture occurred. Radiography indicated that in the copper an internal crack was formed long before the final fracture, the stress decreasing during the growth of this crack. One of the most significant advances in the understanding of ductile fracture was the result of work by Parker, Flanigan, and Davis.3 By the use of etch-pit orientations they were able to demonstrate conclusively that the fracture surface at the bottom of the cup, although on a gross scale normal to the tensile axis, did not consist of cleavage facets as had been previously supposed by many investigators. Recently, Forscher4 has shown evidence of porosity near the tensile fracture of hydrogenated zirconium which he attributes to hydride decomposition. The workers at the Titanium Metallurgical Laboratory5 have also shown evidence of porosity in a number of the commonly used metals after heavy deformation. Many metals have relatively low ductility during creep tests at high temperature. The fractures are intercrystalline, resulting from the nucleation and growth of grain boundary voids. The work in this area has been recently reviewed by Davies and Dennison.6 It is possible that some of the observations and conclusions may have a bearing on the present study? especially since at least two studies7,' have been extended down to room temperature and below using magnesium alloys. However, since magnesium does exhibit low-temperature cleavage, these results may not be pertinent to the present one. The use of the electron microscope as an aid to the study of fractures has been extensively exploited by Crussard and coworkers.9 The examination of direct carbon replicas of the fractures of a large number of metals and alloys showed that the bulk of the fracture surface was covered with cup-like indentations of the order of 1 to 2 µ in size. These frequently had a directionality by which Crussard claims to be able to tell the direction of the crack propagation. With this rather disconnected background of information, this investigation was undertaken in the hope of presenting a unified picture of the initiation and propagation of a fracture in a ductile metal. To this end all of the techniques previously used were employed simultaneously so that there might be a good correlation of the data obtained by different techniques. EXPERIMENTAL PROCEDURE The metal which was chosen as the starting material for this investigation was OFHC copper. Of the dozen or so materials considered, it best fulfilled the requirements of commercial availability in large sizes, good ductility, relatively high melting point compared with room temperature and

Jan 1, 1961

By R. T. Hukki

This paper presents a series of equations for mechanical ball wear, relating parameters of ball size, mill speed, and mill diameter. The fundamental equation, Eq. 12, presented here is introduced to correlate these basic parameters and thus define and clarify the concept of ball wear. This equation is offered as a general rule, which may be modified to apply to individual problems of grinding. BALL wear as observed in grinding installations is the combined result of mechanical wear and corrosion. Corrosion should be a linear function of the ball surface available. Ball corrosion, however, has been studied so little that its effect, although of great importance, cannot be included in the analyses given here. In a separate paper' it is shown that 1 n = 0.7663 np----=— rpm [1] vD P = c, np D kw [2] T=c²(np)n De tph [3] In these equations n — actual mill speed, rpm np = calculated percentage critical speed D = ID of mill in feet P = power required to operate a mill, kw T = capacity of a mill, tph C¹ and c² - appropriate constants in = exponent of numerical value of 1 5 m 1.5 Exponent m is the slope of a straight line on logarithmic paper relating mill speed (on the abscissa) and mill capacity (on the ordinate). It is generally accepted, although not sharply defined, that ball wear in mills running at low (cascading) speeds is a function of the ball surface available. Accordingly, the wear of a single ball may be considered to be a homogeneous, linear function of its surface and of the distance traveled. Thus dw = f¹(d2) . f2(ds) [4] where dw is the wear of a single ball in time dt, d the diameter of the average ball in ball charge, and ds the distance traveled by the ball in time dt. Indicating that ds - a D n dt, the wear of the average ball in time dt becomes dw = f¹(d2) . f2(Dn dt) 1 --- f¹ (d1) f² (D c3 np-----— dt) \/D = c,d² n, D dt The rate of wear of the average ball is given by dw/dt. dw/dt = c, d² np D lb per hr [5] The weight of the ball charge per unit of mill length is a function of D The number of balls of size d in the ball charge is = f³(D2)/f4(d³). The rate of wear of the total ball charge equals the number of balls times rate of wear of the average ball. Thus rate of total ball wear = — . (dw/dt) w. c, . (l/d) . n,, D lb per hr [6] which is the equation of ball wear in low speed mills. In a mill running at a low speed, grinding is the result of rubbing action within the ball mass and between the ball mass and mill liners. When the speed of the mill is gradually increased toward the critical, the impacting effect of freely falling balls becomes increasingly prominent in comparison with the rubbing action. Reduction of ore takes place partly by rubbing, partly by impact. The share of the freely falling balls in the reduction of ore reaches its practical maximum at a speed somewhat less than the critical; at that speed grinding by rubbing has decreased to a low value. It may be reasonable to think that size reduction by freely falling balls should reach its theoretical maximum at the critical speed, if the fall of the balls were not hindered by the shell of the mill beyond the top point; grinding by rubbing would cease at the critical speed. As a first approximation, wear of freely falling balls may be considered to be a homogeneous, linear function of the force at which they strike pieces of rock and other balls at the toe of the ball charge. The force equals mass times acceleration. The mass of a ball is a function of d3 and its acceleration is a function of the peripheral speed of the mill. The wear of a single ball of size d representing the average ball in a ball charge will therefore be w¹ = f3(F) = f (d3) f7 (v). [7] Indicating that v = D n, and n = c³ np 1/vD, Eq. 7 becomes W1 = cn d3 np Do.5 lb per hr. [8] Total wear of the ball charge equals number of balls times the wear of the average ball. Number of

Jan 1, 1955

THE strike of the coal miners began on April 1, as had been expected, the entire force of unionized miners-both anthracite and bituminous-going out and making this the most widespread strike of record. Up to the present writing there has been no serious inconvenience to industry in general, the accu-mulated stocks of coal being large and the non-union mines having continued to make a substantial production. However, the union labor leaders, having concentrated their efforts toward inducing the non-union miners to go out also, met with some measure of success in certain fields and created a shortage of coking coal, which caused iron makers to bank a few furnaces. The strike of textile workers in New England spread further. Here and there, throughout the country there were sporadic troubles with the builders. Rail-way labor was the subject of continued palavers, which did not get anywhere. On the whole the events of April were in line with the forecast that this would be a year of labor troubles. In domestic politics, the soldier bonus bill, having been passed by the House, went to committee consider-ation in the Senate. Public opposition to it manifestly waxed. On the floor of the Senate the tariff bill was under consideration and is drawing nigh to passage, without there being much consideration of its probable economic consequences. It is going to be a very high tariff and there is much in it that is equivalent to subsidizing small and normally unprofitable industries at the expense of the people as a whole. Abroad affairs were more quiet, superficially at least; than they were in March. In Egypt, India and South Africa things calmed, down, so far as we know, but in Ireland there was continued turmoil. The Irish, having won their freedom to the same degree as the Canadians, have entered upon violent quarrels among themselves, more over phrases than anything .else, so far as we can see. Lloyd George obtained a spectacular vote of confidence from Parliament and thus postponed, the exigency of a general election.

Jan 5, 1922

By Dwight C. Roberts, Stender Sweeney

The spacing of wells in Long Beach oil field has caused much discussion from the earliest days of its development, on account of the closely drilled town-lot areas which have been as intensively developed as any productive areas in the world. The purpose of this paper is to present the results obtained from this type of development in comparison with the more widely spaced development in this field, now that a sufficient length of productive life has elapsed. The intensity of development in Long Beach is indicated by the fact that up to Sept. 1, 1929, there were 1736 wells either drilled or drilling. Of these 165 failed to get production and 121 were drilling. Thus 1450 wells have produced oil from an area of 1350 acres. Up to July 1, 1929, these wells produced a total of 35.5,047,913 barrels. Method Pursued Four groups of offset areas were chosen, in each group the wells in one area are widely spaced and in the other, closely spaced. The areas in each group are contiguous and the groups are spread over the field from the southeast end to the northwest, so that representative data are assured. The comparison has also been extended to shallow and deep zones, like zones in their respective areas being compared. Even though these productive zones are very thick, a fair picture of results is obtained, because the drilling of the wells in the two types of areas was concurrent in the different groups and, as a rule, the thickness of sand opened up at any one time was about the same. As deeper sands were found, wells in offset areas were deepened or new ones were drilled in both types of areas. The division of zones was made in the same manner in contiguous areas. The total cumulative production up to July 1, 1929, of the wells in their respective zones in each area was obtained. From these figures were computed the recovery per well, recovery per acre, acreage per well, and the ratios of these factors. Thus July 1, 1929, is the end of the period considered in all areas.

Jan 1, 1930

By A. Gemperle

Electron diffraction and transmission electron microscopy on foils at room temperature were used to investigate the ordering of Fe-Si alloys containing 10 to 23 at. pct Si. A certain degree of DO3 order was found in all alloys. With the exception of the lowest silicon concentration for which the antiphase domains could not be clearly resolved, the alloys have a domain structure of two-domain type with boundaries having 1/4a01<111> displacement vectors for less than 12.3 at. pct Si and with boundaries having 1/2 a0<100> displacement vectors for more than 12.3 at. pct Si. The alloys with 12.3 at. pct Si have a domain structure consisting of fine domains with 1/2a&apos;o<100> boundaries within much larger domains with 1/4a&apos;o<111> boundaries. The development of these structures can be explained by transition of the alloy from the disordered state into the B2-type order and then into the D03-type order by the mechanism proposed previously for the FeSAl alloys. The existence of the B2 structure in the lower part of the investigated concentration range reported in some articles can be explained by fine domains with 1/2a&apos;o<100> boundaries formed by several disordered planes within large domains with 1/4a&apos;o<111> boundaries. The ordered structure predicted by the theory —with practically no domain boundaries —is found in the alloys having 12.3 at. pct Si where it develops in the B2 structure region. ORDERING in Fe-Si alloys was first studied by phragmenl who found that beginning with 13 at. pct Si the DO3 (Fe3Si) superlattice reflections appear in the diffraction patterns. The equilibrium diagrams constructed later by corson2 and Haughton3 from various measurements proposed the existence of a homogeneous solid solution (a phase) in the range from 0 to 25 at. pct Si. Jette and Greiner4 and Farquhar et al.5 measured the relation between lattice parameter and composition and they considered the break in the curve at 9 to 10 at. pct Si to be caused by the ordered solution a"(Fe3Si). Glaser and Ivanick6 Determined critical ordering temperatures of the alloys containing from 10.9 to 27.9 at. pct Si from the measurement of the electric resistivity of quenched samples. In all cases the critical temperature was lower than the melting point and it was highest for 25 at. pct Si. Lihl and Ebel7 measured the lattice parameter curves at various temperatures up to 1000°C. The region between two breaks on these curves, corresponding to 10 to 12.5 at. pct Si at room temperature, was considered by them to be two-phase (a + a"). They concluded by extrapolation of the measured values that a" in the alloy having 25 at. pct Si is stable up to the melting point. Davies8 studied superlattice reflections in the X-ray diffraction patterns of an alloy containing 8.7 at. pct Si. He found the B2 structure and short-range order in the slowly cooled samples and the DO3 A. GEMPERLE is Research Scientist, Institute of PhysicS, Czechoslovak Academy of Sciences, Prague, Czechoslovakia. __Manuscript submitted January 2, 1968. IMD structure in the quenched and annealed samples. This investigation first reports the presence of the B2 structure, phase a&apos;: in Fe-Si alloys. Meinhardt and krisement9,10 also found its existence in Fe-Si alloys by neutron diffraction. No order was detected by them in the alloy containing 8 at. pct Si. The onset of B2 order was observed at a composition of 9.2 at. pct Si. They found almost perfect B2-type order with partial DO3-type order at room temperature in the 10 to 12.5 at. pct Si range and almost perfect DO3-type order in the 12.5 to 25 at. pct Si range. They established the critical temperatures Tc of both the structures through measurement at higher temperatures. The critical temperature for the B2 structure was found to be always higher than the critical temperature for the DO3 structure of the same alloy. They extrapolated the curves of the critical temperatures and concluded that the alloys with more than 17 at. pct Si have the B2 structure up to the melting point and the alloys with more than 23 at. pct Si have the DO3 structure up to the melting point. The results of Meinhardt and krisement9,10 were confirmed by Dokken&apos;s measurement" of the temperature dependence of the electrical resistivity in the 10.8 to 15 at. pct Si range. On the other hand chessin12 detected by X-ray diffraction a considerably lower degree of order in the 12.7 at. pct Si alloy. ANTIPHASE DOMAIN STRUCTURE IN ALLOYS WITH B2- AND DO$-TYPE ORDER The ordered structures B2 and DO3 can be described in terms of a subdivision of the bcc lattice into four fcc sublattices with a parameter double that of the bcc lattice. Following Marcinkowski13 we will label them I. 11, 111, IV. The B2 structure in the AB alloy is formed by placing A atoms on sublattices I and II and B atoms on sublattices III and IV. In a non-stoichiometric perfectly ordered alloy having concentration (A) > (B), A atoms occupy sublattices I and 11. and A and B atoms distributed at random occupy sublattices III and IV. The DO3 structure in an A3B alloy is formed by placing A atoms on sublattices I, 11, and 111, and B atoms on sublattice IV. In a nonstoichiometric, perfectly ordered alloy having concentration (A)/3 > (B), A atoms occupy sublattices I, 11, and 111, and A and B atoms distributed at random occupy sublattice IV. As further shown in Ref. 13, two types of domains are possible in the B2 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4 a&apos;o<ll1> only. Four types of domains are possible in the DO3 superlattice and the antiphase domain structure has associated with it boundaries with displacement vectors 1/4a&apos;o<111> and 1/2a&apos;o<l00>. Bethe14 suggested on the basis of theoretical considerations that in a structure with two sublattices at low temperatures only one domain should be present in the whole crystal at equilibrium. Similarly Bragg15 concluded that at low temperatures the domain struc-

Jan 1, 1969

By D. H. Polonis, Gary A. Dreyer

This investigation involved a study of the reactions occurring during aging of supersaturated a phase in a CIL-Si alloy. The aging processes at temperatures below 552°C were studied by means of metallography, microhardness, and electrical resistivity measurements. During the initial stage of aging in the temperature range 275o to 525oC an anisotropic phase, which is visible in the form of striations in the micro-structure formed prior to the appearance of the -phase. This transition phase has been designated k&apos; due to its structural similarity to the k phase. The rate of K&apos; formation during aging increased with aging temperature. At 450o and 525°C the reaction appeared to reach completion before significant amounts of precipitation were observed. The overall precipitation reaction in this system involved four stages: formation of formation of at a grain boundaries, growth of particles in 7-egions, and coagulation of into large particles. The relative role of each of these processes is dependent on the temperature of aging. The formation of phase from supersaturated a during aging increases the electrical resistivity and slightly increases the hardness of a 4.9 pct silicon alloy. The formation of during aging decreases the electrical resistivity and increases the hardness until coalescence of particles begins during the final stages of aging. The coalescence of results in a decrease of both electvical resistivity and hardness. THE available literature does not record a detailed analysis of the aging processes in Cu-Si alloys. Such an analysis has been difficult due to both the limited data available and misleading microstructural observations which have been reported. Previous work suggests that a rather complicated series of processes may be involved in the aging of supersaturated a. The present investigation is concerned with an analysis of the sequence of these aging processes in a 4.9 pct Si alloy. The currently accepted version of the Cu-Si equilibrium diagram, Fig. 1, was published by C. S. Smith in 1940.&apos; This diagram shows a eutectoid at 5.2 pct Si with the high temperature phase, having its composition range entirely to the right of this value. By quenching alloys in the composition range 4.6 to 5.2 pct Si from the region, Smith was able to retain the phase. However, this phase exhibited a striated microstructure which was anisotropic to polarized light. These striations were suggested by Smith to be duplex twins. Using an oscillating crystal X-ray method Barrett2 studied alloys containing 4.0 to 5.4 pct Si quenched from the and regions. The striations observed in quenched specimens were attributed by Barrett to quenching stresses. He found that striations could also be formed by deformation after quenching and identified them as stacking faults in alloys containing 4.0 to 5.0 pct Si. Barrett related the striations in alloys containing 5.0 to 5.4 pct Si both to stacking faults and to a metastable phase which he called The striated structure reported by smith&apos; was also obtained by Hoffmann, et al. 3 By deeply etching their specimens the anisotropic phase on the surface was removed, leaving a structure which was microscopically similar to pure copper. By means of X-ray analysis before and after deformation at room temperature it was concluded that the anisotropic phase was metastable This conclusion has been questioned by Barrett who attributes the discrepancy to superposition of k and lines on the powder patterns of Hoffmann, et alm3 The decomposition of supersaturated according to smith&apos; and Anderson,4 is very sluggish. However, Nony and Dreyer,5 and Hoffmann, et al.&apos; found that deformation increases the rate of decomposition. X-ray studies by Hoffmann, et al on

Jan 1, 1962

By W. C. Winegard, J. E. Gruzleski

The stages in the development of cells in the Sn-Cd eutectic have been studied by unidirectionally solidifying specimens under known conditions of growth rate, temperature gradient, and impurity concentration. By means of a quenching technique, the shape of the solid-liquid interface during solidification could be observed. Cells are shown to develop from defects or depressions which exist on the solid-liquid interface of even a pure eutectic. Th,e container wall, grain boundaries , and fault lines in the micro structure play an important role in cell development. A two-phase eutectic dendrite found at high impurity concentrations is described. L HE cellular or colony structure formed during eutectic solidification caused much confusion among early workers in their attempts to classify eutectic structure, and a major advance in our understanding of eutectic solidification was made when the colony structure was identified with a cellular interface caused by the presence of impurity elements.1&apos;2 To date, however, no detailed investigation of the stages in cell development in eutectics has appeared, and little work has been done on the cell morphology. The present paper presents the results of such an investigation. EXPERIMENTAL The Sn-Cd eutectic was used in this investigation with lead as the impurity element to promote cell formation. Materials of 99.999 pct purity were zone-refined to an approximate purity of 99.9999 pct. Alloys as close as possible to the eutectic composition, 67.75 wt pct Sn, were prepared using zone-refined tin and cadmium. The alloys were then zone-melted to the exact eutectic composition, as described by Yue and Clark,3 using a total of twenty to twenty-five passes on each eutectic bar. Only those portions of the bars which contained no primary phases were used in subsequent experiments. Master ternary alloys were prepared by melting together the required amounts of lead and the Sn-Cd eutectic in a sealed Pyrex tube under argon, and these alloys were then diluted with pure Sn-Cd eutectic as required. Unidirectional solidification was conducted vertically upward using the two-element resistance furnace shown schematically in Fig. 1. With this apparatus, it was possible to obtain a range of growth rates and temperature gradients so that the cell structure could be studied under different growth conditions. Growth rates in the range of 0.4 to 9.1 cm per hr and temperature gradients from 2.25° to 1475°C per cm were used. To ensure steady-state solidification, power to the furnace was stabilized, and the entire apparatus was enclosed in a large box in which the temperature was controlled to within ± 0.2°C. The apparatus was arranged so that the specimen could be quenched in situ during solidification by pouring a large quantity of water down the central vycor tube. Excellent delineation of the solid-liquid interface at the time of the quench was obtained because of the structural changes accompanying the rapid solidification of the remaining liquid. The quenching rate was always extremely rapid as no evidence of a transition in the lamellar spacing at the interface was ever observed. The alloys to be solidified were contained in degassed, high-purity graphite tubes, 1 cm OD and 0.6 cm ID. The specimens were about 18 cm in length. After the alloy had been cast into the tubes, three 0.8-mm holes were drilled in the tube to the center of the specimen. One hole was placed 1 cm from the bottom of the ingot, and the other holes were placed at 8 and 9 cm, respectively, from the base of the ingot. Thirty-four-gage chromel-alumel thermocouples were sealed in the holes. The lower thermocouple was used to position the solid-liquid interface at the start of each experiment,

Jan 1, 1969

By G. S. Cole, G. F. Bolling

Recent experitnents on crystal growth have indicated that thermal convection in the liquid influences the conditions of solidification and subsequent crystal characteristics. However, the important columnar-equiaxed transition in castings has not been examined as a function of this free convection. An experiment is presented here to demonstrate a change in the transition as convection is suppressed. Lead- and tin-based alloys were cast in stainless-steel molds either without special procedures or with thin grids placed horizontally across the tnold diameter in portions of the castings. While the grids allowed some diffusion of heat and mass transport to occur during solidification, massive fluid flow was hindered in the vegiotz of the grids. A larger percentage of columnar grains appeared in the grid region than in other parts of the special castings or than in all regions of normal castings. This structural difference can be explained in terms of thermal convection. THERE is little information about the possible effects of natural convection which may occur during the solidification of a casting. Ruddlel-3 has stated that the movement of liquid metal produced by convection might assist in the transfer of heat, but in the absence of confirmatory evidence he suggested that this idea be treated with caution. chalmers4 considers, but does not assess, the importance of fluid motion in casting, while Tiller5 suggests that, in liquid metals which have extremely high thermal diffusivities, the effects of thermal convection may be negligible. In addition, throughout the literature, there are statements indicating the possible presence of thermal convection but without proofs or evaluations of its influence. Natural convection may be divided into two categories: thermal convection, where liquid flow is due to density differences caused by temperature gradients in the liquid (e.g., liquid near a cold wall falling with respect to hotter liquid further away from the wall); and solute convection, where flow is due to density differences as a result of concentration gradients, see Wagner.6 In most instances thermal convection predominates over solute convection. Nevertheless, even thermal convection has not been studied in any detail and is difficult to handle, since it can vary quantitatively from one experiment to another depending upon the exact positions of heat sources and sinks or the attitude of the container with respect to gravity. In spite of these difficulties it is possible to realize that a higher rate of heat transfer must result with convection than in any situation where conduction acts alone. Thus, the degree of increased heat transfer is the important undecided question in considerations of casting. It will be demonstrated here that a reduction in convective flow leads to a suppression of the columnar-equiaxed transition in a casting and that this suppression is related to a decrease in the degree of heat transfer. Fortunately it is possible to do this by comparative rather than quantitative measures. The insertion of horizontal plates or grids into a simple mold does not appreciably influence heat transfer per se, but in reducing the allowable height through which colder liquid may fall freely it reduces natural thermal convection. This leads to a reduced fluid velocity, a different flow pattern, and an altered heat transfer which can be measured. EXPERIMENTS The alloys were prepared from elements of 99.9 pct nominal purity and cast into an uncoated 2-in.-diameter stainless-steel mold insulated at the bottom with a suitable refractory so as to ensure predominantly radial heat flow during freezing. Casting was performed either in empty molds or in molds containing grids or plates in various configurations . The grids were constructed of aluminum screen (1/32 in. thick) which was cut to the desired shape, cleaned in aqua regia, and coated with a mixture of 2 parts aqua dag graphite -1 part Sauereisen cement mixture, thus supplying a hard, protective, and insulating layer approximately 0.006 in. thick. The

Jan 1, 1965

The authors of T.P. 4179 have conducted a large number of experimental water floods, and the data are reported in a very clear manner. These data show significant variations of residual oil saturation with changes in wettability, interfacial tension, flooding rate, and oil-water viscosity ratio. Furthermore, some of the data obtained cover a range of variables not previously reported in the literature. It is our opinion that at least some of the observed variation in oil recovery can be obtained only in floods made under conditions identical with those used by the authors. There are other systems which may be said to have the same wettability, but which exhibit an entirely different qualitative dependence of oil recovery on the experimental variables. In this regard, we would like to direct attention to several items which we feel are not given sufficient consideration in the paper. The first of these items has to do with wetting equilibrium. A survey of the current literature will reveal that little is known, and even less is understood, about wetting equilibrium. This is particularly true of the relation between contact angle measurements made under static conditions, and the wettability existing under the dynamic conditions of floods carried out at relatively high rates. We feel that this is a very important consideration, particularly in the floods the authors performed under what they consider to be "water-wet" conditions. It is our opinion that wetting equilibrium did not exist in these floods, except possibly at the very lowest rates. This opinion is in part based on some flooding tests we have made which are very similar to some of those described by the authors. These floods were made in unconsolidated cores, 6 in. long and 13/4 in. in diameter, made up of carefully graded glass spheres of the approximate size of the sand grains used in the subject paper. The cores were mounted vertically, and distilled water was used to displace a refined oil equivalent to the authors Soltrol C. The glass spheres had previously been carefully cleaned so that they were strongly wet by the water. The floods were made with and without an interstitial water saturation. When interstitial water was present, the solid surfaces were mostly covered with water prior to injecting the flooding phase. Consequently, a condition very near wetting equilibrium existed throughout the flood. The data in Fig. A show that under these eircumstances, rate had no influence on residual oil at flood-out, over the range of rates studied. On the other hand, in the absence of interstitial water, the surfaces are all covered with oil before the displacement. To achieve wetting equilibrium the injected water must displace the oil from the surfaces themselves. This is not a fast process. Therefore, the effective dynamic wetting condition in floods of this type must depend upon the flooding rate. When the flood rate is very low, compared to the rate at which wetting equilibrium is attained, the residual oil saturation at flood-out is essentially the same as the residual obtained when interstitial water is present. This is shown in Fig. A, and occurs because the dynamic wetting conditions are the same in both cases. However, at moderately high flooding rates, the rate has an important bearing on the amount of oil recovered because in this case the attainment of surface equilibrium is the slow step. We believe that, in the absence of an interstitial water saturation, oil recovery varies with rate because of the reasonably slow approach to wetting equilibrium which occurs during the displacement. In fact, as the rate is increased, the oil recovery performance indicates the core is becoming progressively less water-wet. At the highest rate there is even considerable simultaneous production of oil and water after breakthrough. This does not occur at the lower flooding rates, nor is there appreciable simultaneous oil and water produc-

Jan 1, 1957

Jan 1, 1926