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By E. T. Turkdogan, J. H. Swisher

bi the fivst part of the paper results ave given on the rate of decarburization of Fe-C melts ln CO2-CO atmospheres at 1580°C. The rate -controlling step is believed to he that irvlloluing dissociation of curbotz dioxide on the suvfuce of the melt. 4 genevral reaction mechanistm is poslnlated jor gels-t11eta1 veactions oc-curit~g on the surface of iron coutcotamncited with chemi-sovbed osygesL. Oxygen the present work on decavbuvization of liquid iron and previous studies on the kinetics of nitrogen absorption and desorplion are discussed in terms of the postulated mechanism, ManY of the early studies of rate of decarburization of liquid steel were of an exploratory nature and laboratory exppriments carried out pertained to open-hearth or oxygen steelmaking processes. References to previous work on this subject may be found in a literature survey made by Ward. Using more sophisticated experimental techniques, several investigators have recently studied the kinetics of decarburization of molten Fe-C alloys in oxygen-bearing gases. For example, Baker et al2.' reported their findings on the rate of decarburization of liquid iron, levitated by an electromagnetic field, in carbon dioxide-carbon monoxide-helium atmospheres. In these levitation experiments the samples used were small in size, e.g., -0.6-cm-diam spheres weighing -0.7 g, and the rates were measured for decarburization from about 5 to 1 pct C at 1660°C. The rates obtained under their experimental conditions were considered to be controlled primarily by gaseous diffusion through the boundary layer at the surface of the levitated melt. Parlee and coworkers3 measured the rate of absorption of carbon monoxide in liquid iron. The rates were found to follow first-order reaction kinetics, yielding a reaction velocity or a mass transfer coefficient in the range 0.2 to 0.4 cm per min. The coefficient was found to decrease with increasing carbon content of the melt. These investigators attributed the observed rates to the transfer of carbon or oxygen through the diffusion boundary layer adjacent to the surface of the melt. In the work to be reported in this paper, an attempt has been made to study the kinetics of gas-metal surface reactions involved in the decarburization of liquid iron. EXPERIMENTAL The experiments consisted of melting 80-g samples from an Fe-1 pct C master alloy in an induction furnace and decarburizing in controlled CO2-CO mixtures at 1 atm pressure and 1580°C. The master alloy was prepared by adding graphite to electrolytic "Plastiron" melted in racuo. None of the impurities in the master alloy exceeded 0.005 pct. The reacting gases were dried by passage through columns of anhydrone; in addition, CO2 impurity in carbon monoxide was removed by passage through a column of ascarite. A schematic diagram of the apparatus is shown in Fig. 1. A 1.25-in.-diam recrys-tallized alumina crucible containing the sample was placed inside a 3-in.-diam quartz reaction tube, all of which was surrounded by an induction coil. A 450-kcps induction generator was used as the power source. Water-cooled brass flanges, which contained the gas inlet, gas exit, and sight port, were sealed to the top of the reaction tube with epoxy resin. The reacting gases were metered with capillary flowmeters and passed through a platinum wire-wound alumina preheating tube, 0.25 in. ID and 11 in. long. The gases were preheated to about 1300°C. A disappearing-filament optical pyrometer was used to measure the melt temperature. The pyrometer was initially calibrated against a Pt-6 pct Rh/Pt-30 pct Rh thermocouple. The temperature was controlled to within +10°C by manually adjusting the power input to the induction coil. In a typical experiment, an 80-g sample of the master alloy was melted in a CO2-CO atmosphere having pcO2/pco = 0.02 and flowing at 1 liter per min. A negligible amount of carbon was lost and no significant reduction of alumina from the crucible occurred during melting, e.g., 0.005 pct Al in the metal. After reaching the experimental temperature of 1580°C, the gas composition was changed to that desired for a particular series of decarburization experiments. The duration of the transient period for obtaining the desired gas composition at the surface of the melt was about 20 sec . The flow rate of the reacting gas was maintained at 1 liter per min. After a predetermined reaction time, the power to the furnace was turned off. During freezing, which took about 10 sec, the amount of gas evolution was not sufficient to result in a significant loss of carbon. The samples were analyzed for carbon by combustion and in a few cases they were analyzed for oxygen by the vacuum-fusion method. RESULTS A marked increase in the rate of decarburization of iron with increasing pcO2/pco ratio in the gas stream is demonstrated by the experimental results given in Figs. 2 and 3 for pco2/pco ratios from 0.033 to 4.0. In one series of experiments, denoted by filled triangles in Fig. 2, the reacting gas was diluted with argon (48 vol pct) resulting in a slower rate of decarburization. Samples from two series of experiments with pco2/pco = 0.033 and pco2/pco = 0.10 (with argon dilufion) were analyzed for oxygen. In these Samples the oxygen content increased with reaction time

Jan 1, 1968

By E. J. Roberts

F. C. Bond (Allis-Chalmers Mfg. Corp., Milwaukee) —This paper considers comminution as a first order process, with the reduction rate depending directly upon the amount of oversize material present. The data show that other factors should be taken into account, and it is possible that in time these may be evaluated as simultaneous or consecutive reactions: Development of the theory of comminution has been retarded for many years by the assumption that surface area measurements constitute the sine qua non of the work done in crushing and grinding, and it is encouraging to note the belated growth of other ideas. In the Abstract the term "net power" should be changed to "net energy." Throughout the paper the term "hp per ton" should be changed to "hp hrs per ton", or "hp hr t." The term "Probability Theory" in the title does not seem appropriate, since it is not clear how the probability theory is used in developing the ideas in the paper. There seems to be a contradiction between the large calculated advantages of closed circuit operation and the statement following that the closed circuit test results showed no significant change in grinding behavior, when compared with the batch grind curves. Tables I and II show that between 75 pct and 50 pct solids the energy input required decreases with increasing moisture content and may indicate the advisability of grinding at higher dilutions in certain cases. The calculation of the hp-hr per ton factor indicates an input in the laboratory mill of only 7.32 gross hp per ton of balls; this casts some doubt upon the accuracy of the factor used, since the power input in commercial mills at 80 pct critical speed is customarily much higher. The tests show that within fairly wide limits the amount of ore in the laboratory mill may be varied and a product of constant fineness obtained, provided that the grinding time is varied in the same proportion. This has often been assumed, and confirmation by actual testing is of value. The Cavg corrections for differences between the plant and laboratory size distributions do not seem very satisfactory, since in many cases the plant/laboratory ratio is farther from unity after correction than before. The following equation has been derived from the data in Table VI: Relative Energy (log new ball diam in in. + 0.410) Input = --------------—--------------- from which the relative energy inputs for balls of different sizes can be calculated and compared. The relative energy input is unity for balls of 2.715 in. diam. The equation indicates that the work accomplished by a ton of grinding balls per unit of energy input is roughly proportional to the square root of the total ball surface area; provided, of course, that the balls are sufficiently large to break the material. The data in support of this statement are admittedly meager, but are fairly consistent when plotted. The relative grindability values listed in Table VI for 200 mesh multiplied by 4/5 apparently correspond approximately to the A-C grindability at 200 mesh.' It would seem that for open circuit tests comparable accuracy could be obtained much more simply by the old method' of plotting the test grind, extending the mesh grinds to the left of zero time if necessary, and determining from the plot the equivalent time required to grind from the plant feed size to the plant product size, using the average of several mesh sizes. The en- ergy input value of one time interval could be determined by tests on materials of known grinding resistance, and this multiplied by the interval required should give the desired energy input value. The relative grindabilities would be the relative time intervals required for a specified feed and product size. When the plotted mesh size lines of a homogeneous material are extended to the left beyond zero time they meet at one point at zero pct passing. The horizontal distance of this point from zero time indicates the equivalent energy input required to prepare the mill feed. The author's results show that the closed circuit grinding tests give about the same K values as open circuit tests, from which he concludes that open circuit tests are satisfactory in many cases. The value of the closed circuit test is its ability accurately to predict energy requirements in closed circuit grinding for both homogeneous and heterogeneous materials. If the material is homogeneous, the open circuit test gives satisfactory results; but if the material contains appreciable fractions of hard and soft grinding ore, the open circuit tests will not be accurate because of the accumulation of hard grinding material in the circulating load. Since in most cases it is not possible to determine a priori whether the material contains hard and soft fractions, the closed circuit tests are preferable and more reliable. B. S. Crocker (Lake Shore Mines, Ontario)—Dr. Roberts probability theory of grinding is very similar to our log pct reduced vs. log tonnage method of plotting and evaluating grinding tests at Lake Shore. However, although we both seem to start at the same point we finish with different end results. Shortly after publishing our grinding paper (referred to by Dr. Roberts) in 1939, we did pursue the subject of the "constant pct reduction in the pct +28 micron material for each constant interval of time. We ran innumerable tonnage tests on the plant ball mills, rod mills, tube mills with 11/4 and 3/4 balls, and lastly pebble mills, with tonnage variations from 180 tons per day to 950 tons per day. We found that when we plotted the log of the tonnage against the log of the pct reduced of any reliable mesh, we had a straight line up until 90 pct of the mesh is reduced. We have also tested this in our 12-in. laboratory mill with the same results. We have used this method of evaluating grinds for the past 8 years and developed the recent four stage pebble plant on this basis. By pct reduced we mean the percentage of any given mesh that is reduced in one pass through a mill at a given tonnage (or time). For example, if the feed to a rod mill is 90 pct +35 mesh and the discharge at 500 tons per day is 54 pct +35, the pct reduced is 90 — 54/90 = 40 pct. If the feed had been 80 pct +35 the discharge would have been 48 pct +35 or pct re- duced 80-48/80 = 40 pct as long as the tonnage re- mained constant at 500 tons per day. Thus we can easily correct for normal variation of mill feeds. This log — log relationship derived from the tonnage tests of all our operating mills has proved of tremendous help in checking laboratory work and in designing alternate layouts or new plants. The difference between the log — log and the semi-log plot is only shown up when the extremes in tonnages are plotted. When the relationship between the pct reduced and the tonnage was first investigated, we used semilog

Jan 1, 1952

By John Blatchford, William T. Hall

The product obtained by roasting stibnite is likely to contain some unoxidized antimony trisulphide and a mixture of antimony trioxide and antimony tetroxide. It was desired to determine, as accurately as possible, the condition of the antimony as well as the total quantity present. Attempts were made to separate the trisulphide and the two oxides by methods based upon their varying solubilities in different solvents, but no satisfactory results were obtained in this way. It was found, however, that by determining the total antimony content, the antimony present as trioxide, and the antimony present as trisulphide, a good idea of the chemical composition of the roasted product could be obtained. The total antimony was determined by dissolving the sample in concentrated hydrochloric acid, reducing the antimony entirely to the trivalent condition by means of hydriodic acid and eventually titrating the antimony back to the pentavalent condition by means of iodine in the presence of sodium bicarbonate1* The details of the procedure are as follows: Weigh out 0.25 gram of the roasted product into a trapped flask (Fig. I), add 4 grams of powdered tartaric acid, 2 grams of potassium iodide and 40 c.c. of concentrated hydrochloric acid. Boil the solution gently f;r 5 min. and then cool to room temperature by shaking the flask while holding it under running water. Then, very carefully discharge the iodine color by the cautious addition of 0.05-normal sodium thiosulphate solution, adding a little starch toward the last. Nearly neutralize the acid with ammonia solution, but leave the solution distinctly acid. Pour the slightly acid solution into 200 c. c. of water containing an excess of sodium bicarbonate and titrate to a permanent blue color with standard 0.1-normal iodine solution.

Jan 1, 1916

By E. C. Truesdale, Gerald Edmunds

A few years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.&apos; During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. Table 1.—Typical Analyses Percentnge by Weight Sum of Zinc Fe, Ib1 Fe Cd 1A1 cd Special High Grade*.......... 0.007b 0.005b 0.005b none O.OIOb C.P. (chemically pure)......... < 0.0002 0.0005c 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 637). b Maximum. &apos; Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By E. C. Truesdale, Gerald Edmunds

A few years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.&apos; During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. Table 1.—Typical Analyses Percentnge by Weight Sum of Zinc Fe, Ib1 Fe Cd 1A1 cd Special High Grade*.......... 0.007b 0.005b 0.005b none O.OIOb C.P. (chemically pure)......... < 0.0002 0.0005c 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 637). b Maximum. &apos; Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

By E. C. Truesdale

A FEW years ago H. M. Cyr, working in the Research Laboratories of The New Jersey Zinc Co., produced a few pounds of zinc1 of such purity that no other elements were detected in it by spectrographic analysis, using the facilities then available. This zinc contained less than one ten-thousandth of one per cent of metallic impurities.2 During the decade that followed upon the laboratory production of this "spectro-graphically pure" zinc, commercial developments brought about the production of large tonnages of zinc of purity exceeding 99.99 per cent, and today zinc of 99.999 per cent purity is produced and marketed as "chemically pure" zinc. Typical analyses of present supplies of high-purity zinc are given in Table 1. TABLE 1.-Typical Analyses Percentage by Weight Sum of Zinc Pb, Fe, Pb Fe Cd Al Cd Special High Grades 0.007b 0.005b 0.0056 none 0.0106 C.P. (chemically pure) <0.0002 0.0005° 0.000052 S.P. (spectrographically pure).. <0.0002d <0.00005d a A.S.T.M. Standard Specification for Special High Grade Slab Zinc (A.S.T.M. Designation: B 6-37). b Maximum. c Fe chemically determined. Pb and Cd are spectrographically determined. d Differences between composition of C.P. and S.P. zinc are discussed later in this paper. The availability of commercial tonnages of special high-grade zinc has been the basis for the development of the zinc-base die-casting alloy industry which, in the year 1936, consumed one-eighth of the zinc used in the United States for all purposes. This and the C.P. and S.P. grades have given impetus to scientific investigations into the properties of pure

Jan 1, 1939

Edward K. Landis, Philadelphia, Pa.: In studying Mr. Thackray&apos;s paper it seemed that a critical comparison of the results from different methods therein reported would he of interest. For this purpose Table I. was constructed by grouping all determinations made by the same method, and the probable errors were calculated. In this table all chemists titrating with permanganate (A1, E, F, G and 0 of Mr. Thackray&apos;s paper) are classed under "Emmerton;" those titrating with nitric acid (C, J, S and Y) under " Handy; " those re Probable error of result: a, ±0.0008996; b, ±0.000694; c, ±0.00107; d, ±0.00115; e, ±0.000674; f, ±0.000473; g, ±0.003675; h, ±20.0007959; i,0.000.5098; k, ±0.0008303. Probable error of single determination: a, ±0.001989; b, ±0.001547; c, ±0.00214; d, ±0.0023;e, ±0.00116;f, ±0.000818;g, ±0.0019;h, ±0.00224; i, 40.00143; k, ±0.00234. The formula for calculating the probable error is 0.6745, where N (N— 1)&apos; S is the sum of the squares of the differences from the mean and N is the number of determinations.

Jan 1, 1897

By J. B. Wagner, B. Swaroop

The atomic ratios of oxygen to iron in zlarious corn-posilions of wustite in the vicinity oj the reported p to n transformation were determined in the temperalure range between 950" and 1250°C. For these conditions, equilibrium vacancy concenrations have also been determined at vatious mixtures of C0,-CO. The data show a continuos introduction of iron vacancies as oxygen is introduced into wuistite. No phase change is observed with in the wuustite field. However, the value of n in the isothermal oxygen pressure dependence, the weight change shifts to 1ower values as the concentration of oxygen increases. WUSTITE is a metal deficit semiconductor with the majority lattice disorder being cation vacancies. Using the notation similar to that of Kroger and ink,&apos; the dissolution of oxygen into wiistite using C02-CO mixtures is represented by, WHere v+! denotes a cation vacancy with k effective negative charges and kh • denotes k electron holes, h -. Applying the law of mass action and assuming a dilute solution of defects in the wiistite yields Where the square brackets denote concentrations. Furthermore, when k = 2 the cation vacancies are completely ionized, and both the concentration of cation vacancies and the concentration of electron holes are proportional to the third root of the ratio, PC /PCo. This analysis is valid for one particular mael based on an ideal solution at elevated temperatures (in this case t > 1000°C). At lower temperatures, it has been shown2 that the pressure dependence of the electronic conductivity changes in a manner which suggests that vacancies interact with or "trap" electron holes. At the very high concentrations of defects, 10&apos;&apos; to 10" per cu cm, these simple models no longer hold. Recently Tannhauser,3 Geiger et a1.&apos; Bransky and Tannhauser; and Hillegas&apos; have found an apparent p to n transformation in wiistite in the temperature range of 950" to 1300°C. This junction was found by thermoelectric and electronic conductivity measurements. Geiger eta1.&apos; found that the electronic conductivity became almost independent of the oxygen pressure at high temperatures and oxygen concentrations within the experimental error. In addition, Vallet, Raccah, and coworkers6&apos;7 have reported the existence of several "varieties" of wiistite which were reported to exist within what was heretofor presumed to be a

Jan 1, 1968

GENERAL COMMITTEE GERALD F. G. SHERMAN, Chairman. ARTHUR NOTMAN, Secretary. NORMAN CARMICHAEL, JOHN C. GREENWAY, W. L. CLARK, W. G. McBRIDE, B. BRITTON GOTTSBERGER, FOREST RUTHERFORD. General Committee on Transportation WALTER DOUGLAS, Chairman. CLEVELAND E. DODGE, Secretary. ARTHUR S. DWIGHT, JOHN C. GREENWAY, JULIUS KRUTTSCHNITT, JR. Committee at El Paso W. D. GORDON, ROBERT McCART, JR., W. W. ROSE. Committee at Santa Rita JOHN M. SULLY, Chairman.

Jan 12, 1916

CONTENTS KANSAS-H. S. BRYANT 3 TEXAS, EXCEPT GULF COAST-M. C. CHENEY 14 GULF COAST-L. P. TEAS 21 TEXAS PANHANDLE-W. E. HUBBARD 29 LOUISIANA, ARKANSAS AND MISSISSIPPI L H. K. SHEARER 37 ROCKY MOUNTAINS-R. C. COFFIN 43 CALIFORNIA-V. H. WILHELM 51 MICHIGAN AND THE TRENTON FIELDS OF OHIO AND INDIANA-M. G. GULLEY 65 ILLINOIS, WESTERN KENTUCKY AND WESTERN INDIANA-A. H. BELL . . . 73

Jan 1, 1932

By A. E. Dwight

Lattice parameters were determined for eighteen equiatornic alloys of the CsCl-type structure, ten of which were previously un-reported. It was found that fomation of the CsCl-type structure in binary alloys of the transition elements is largely dependent on position of the elements in the periodic table. The relative size of the two elements was not found to be a controlling factor. A recent paper by Beck, Darby, and Arora1 corre-lates the occurrence of CsC1-type ordered structures with the position of the constituent elements in the periodic table for the first long period. It was also suggested that a definite increase in relative bond strength between unlike atoms occurred when, in binary alloys of iron-group elements, the other component is changed from a chromium-group element, to a vanadium-group element, to titanium. A later paper by Philip and Beck2 noted that the lattice contraction increased in the order CrFe, VFe, and TiFe. It was also noted by Philip and Beck2 that the lattice contractions of CsC1-type alloys decreased in the order: TiFe, TiCo, and TiNi, which is an apparent reversal of the contractions expected from the position in the periodic table. It was suggested that the increasing lattice contraction is an indication of increased stability, i.e., greater A-Bbond strength. The present investigation was carried out to determine whether the relation of the position in the periodic table to the formation of the CsC1-type structure was also correct for alloys involving the second and third long-period elements. A systematic search was made for CsC1-type structures among equiatomic alloys and for those found, the lattice contraction was determined. EXPERIMENTAL TECHNIQUE The elements Y, Gd, Ti, Zr, Hf, V, and Cb are designated the A group and the elements Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au are designated the B group. Equiatomic alloys were prepared for 57 AB combinations. The alloys were arc melted in a multicrucible furnace3 in buttons ranging from 5 to 20 g. Chemical analyses were not made, as the charge weights agreed closely with those of the buttons after melting. The alloy buttons were homogenized at 800° to 900°C. Metal log raphic and X-ray specimens were prepared and heat treated at temperatures from 600° to 1200°C. Specimens for X-ray diffraction were usually ground to a powder in an agate mortar; however, needle-shaped solid specimens were used when the alloy was sufficiently ductile to permit their preparation. Diffraction patterns were taken with a Straumanistype Debye-Scherrer camera using filtered Cu or Co radiation. The lattice parameters were obtained in A by plotting the calculated a0 values against the cos29/sin 0 + cos2?/? function and extrapolating linearly to ?= 900. Metallographic control specimens were polished on cloth wheels with diamond paste and etched with various phosphoric and nitric acid reagents. RESULTS The eighteen equiatomic alloys listed in Table I gave evidence of a cubic structure with two atoms in the unit cell, although two of these cubic structures exist only at elevated temperatures and transform to a tetragonal structure on quenching. Nine of these eighteen alloys gave diffraction patterns with super-lattice lines showing that the structure is of the CsC1-type. The lack of superlattice lines in patterns of the other nine alloys may be attributed to the small difference in atomic scattering power of the components. Metallographic study indicates the occurrence of nine narrow single-phase fields at the AB composition. Any or all of these nine may also have a CsC1-type structure. The VFe alloy was found to have a CsCl-type structure by Philip and Beck2 through the use of CrKa radiation (for which the scattering factor of V is anomalously low), whereas the Cu radiation used

Jan 1, 1960

By John D. Verhoeven

A technique has been developed for carrying out normal freezing experiments with a current density of 2000 amp per sq cut passing through the solid-liquid interface. The equation relating the effective distribution coefficient to the equilibrium distribution coefficient in electric field-aided solidification, originally developed by Huckc et al.,1 has been modified for the case of concentrated solutions. Preliminary experiments on the Sn-Bi system give qualitative agreement with the equation. The data are analyzed by a slightly novel use of the normal freeze equation which allows one to determine the effective distribution coefficient more easily. Very extensive mixing in the liquid was found at these high current densities and it is postulated that the mixing results from a vertical component of the magnetic Lorentz force generated by the electric current. In the search for techniques of obtaining ultrahigh-purity metals the inefficient but very effective technique of electrotransport has received little attention. Electrotransport is most effective in the liquid state and a natural application, therefore, is to apply an electric field across the liquid zone of a zone-melting experiment. The present investigation was undertaken to study the effect of an electric field upon solidification of metals, so that the usefulness of electrotransport in such solidification experiments as zone melting could be determined. In zone-melting and normal-freezing experiments it is difficult to achieve complete mixing in the liquid in the immediate vicinity of the solidifying interface. Consequently a solute build-up will occur at the interface in the portion of the liquid where complete mixing does not occur (an equilibrium distribution coefficient, ko, less than one, and unidirectional atom motion will be implied throughout). This local solute build-up produces a corresponding rise in the solute concentration in the solid so that the ratio of the solute concentration between the solid and the bulk liquid is larger than the equilibrium distribution coefficient. This ratio is defined as the effective distribution coefficient, k,. The differential equation describing the solidification process may be derived by applying the continuity equation to an expression for the net solute flux at the interface. The solution to this differential equation then allows one to determine the solute distribution in the liquid and the relationship between k0 and ke. One of the most useful solutions to this equation was first derived by Burton, Prim, and Slichter,&apos; in which they assumed that a) the equilibrium distribution of solute was maintained on the plane of the interface, 11) the solute build-up ahead of the interface in the liquid disappeared at a distance 6 from the interface, and c) the solute distribution in the liquid was invariant with time. The following well-known relation between ko and ke was then obtained, where R is the rate of solidification and D the diffusion coefficient of the solute in the liquid. This equation appears to correlate the data from a number of different types of solidification experiments very well. Application of an electric field across the solid-liquid interface can produce an additional flow of solute atoms as a result of the electrotransport. When the polarity of the field is such as to direct the electrotransport flux away from the interface the solute build-up may be diminished, even to the point of producing a solute depletion and a consequent ke smaller than ko. The quantitative description of this process and the resulting form of Eq. [I] was first given by Hucke et al.1* and then inde- where E is the electric-field intensity and U is the differential mobility, i.e., the velocity of the solute atoms with respect to the solvent atoms per unit electric field. Both authors follow the method of Burton, Prim, and Slichter in their derivation, the only difference being the additional electrotransport term in the flux equation. It has been pointed out1,3 that Eq. [2] predicts the possibility of a noticeable increase in the purification of materials by solidification in an electric field. The validity of Eq. 121 has not been checked experimentally and it is possible that other factors&apos; arising from the presence of an electric field across

Jan 1, 1965

By W. Jolley

Decarburized iron and Fe-3.28 pct Ni alloys were impact and tension tested in the temperature range of ambient to 4°K. It was found that alloying with nickel improves the fracture properties of the ferrite matrix. The improvement in toughness of iron alloyed with nickel is attributed to the effect of the nickel addition on the temperature and strain rate dependence of the yield stress as well as on slip behavior. The Fe-Ni alloy exhibits wavy slip when strained at temperatures down to at least 50°K. This behavior contrasts with that of the unalloyed iron where a change It is a generally accepted fact that of the common alloying elements of steel only nickel and manganese improve both the room-temperature yield strength and the notch impact properties. It has been argued for a number of years that manganese refines the ferrite grain size, the pearlite spacing, and the grain boundary carbides in medium- and low-carbon steels and thereby increases resistance to brittle fracture.&apos;&apos;&apos; This hypothesis recently was confirmed for a 0.04 pct C iron containing manganese, but at the same time from wavy to planar slip occurs at about 120°K. The observed lower temperature and strain rate dependence of the lower yield stress in the Fe-Ni alloy as compared to the unalloyed iron may be attributed to this difference in slip behavior. In contrast to suggestions published previously, transmission electron microscopy showed that the uniform dislocation distributions and the lack of dislocation tangles which are produced by low-temperature straining of bcc materials cannot be attributed to the absence of cross slip at these temperatures. no increase in notch toughness was observed in a decarburized Fe-Mn alloy.3 It thus appears that manganese only increases the toughness of Fe-Mn-C alloys by refining grain boundary carbides and has no toughening effect in carbon-free iron. On the other hand, the mechanism whereby nickel improves toughness has not been established. Hodge et a1.4 have clearly shown that a 3.28 pct Ni addition lowers the impact transition temperature of 0.02 pct C steel approximately 35°C when the grain size is maintained constant. Recently, Wullaert and Tetelman6 stated that nickel refined the grain boundary carbides of an Fe-C alloy and consequently increased the toughness. They also observed the previously reporteda-&apos;

Jan 1, 1969

By G. R. Love

i\ program has been written which allows fully automatic conversion of data for X-ray intensity, as a function of time, to finished conventional pole figures. The program accepts input data in the serial order in which they are taken and is therefore immediately compatible with automatic data-acquisition devices. From these data taped instructions are prepared for the Calcomp plotter to construct ink-on-paper drawings. Because both Siemens and Norelco pole figure goniometers are used in this laboratory, the program was written for pole figure data obtained from one or more interpenetrating spiral scans during which both the polar angle, @, and the equatorial angle, a, are varied simultaneously and continuously. The reference direction for a scan, that is the point @ = 0 deg, may be chosen coincident with either the normal direction (N.D. figures) or the rolling direction (R.D. figures). In either case the plotted figures are drawn with the transverse direction (a = 0 deg) at the right and the rolling direction at the top. The full, circular, pole figure is drawn as two semicircular figures labeled "front side" and "back side". As presently constituted, the program will also accept data from circular scans taken at constant values of @. In every case the angular coordinates of each intensity entry are generated in the computer from a relatively small number of auxiliary data. The X-ray intensity data are corrected for background scattering by direct subtraction of the intensity measured with 28 set appropriately "off" the Bragg angle. It is possible to enter this correction as an additional spiral scan through the a, @ space; because the background correction does not normally vary rapidly enough to warrant this detailed a determination, the background corrections are entered as one or more auxiliary data. All data are normalized to a multiple of random intensity. The data taken in this laboratory for N.D. figures are normally taken in a reflection geometry from from sheet samples and do not extend beyond <p = 75 deg; for these data random intensity must be determined from separate experiments and entered as auxiliary information. When the auxiliary information is not available, a number is chosen to give intensity values normalized to a scale of 1 to 10. In this laboratory, R.D. figures are based upon hemispherical samples for which data are taken out to @ = 90 deg; for these data random intensity is calculated by direct numerical integration of . sin @ d@ using the trapezoidal rule and the background-corrected values of the input data. Points necessary to the construction of the pole figure are identified by simple linear interpolation between adjacent data points to determine the loci of contour lines. Points lying on a given contour are connected to one another with straight-line segments and the search-calculation-drawing sequence is patterned to assure that different contour lines do not cross, that a single line does not branch, and that lines do not end in space. However, so that there be no ambiguity in the data presentation, all contour lines end at the limits of the input data. Since the curves are constructed of straight-line segments, they are not continuous in their derivatives. However,

Jan 1, 1969

By T. D. Tiemann

The extraction of iron oxide from several types of siliceous iron ore by digestion in sulfuric acid solutions was investigated in the temperature range from 80 to 258°F at concentrations from 10-60% H2SO4. Degree and rate of extraction were found to be critical with respect to both temperature and acid concentration, requiring temperatures in excess of 250° F and acid concentrations of 50% to effect 80-90% extraction of iron oxide in 60 min. Rate of extraction is directly related to surface area and apparently controlled by the rate of chemical reaction. The activation energy was found to be approximately 25,000 cal per g mol. Extraction characteristics of the several ores were found to be similar. The Department of Minerals and Metals Engineering at the University of Wisconsin conducts a continuing research program to develop processes for the utilization of low-grade iron ore deposits such as the nonmagnetic taconites of the Wisconsin Gogebic range. Methods under study include high-intensity magnetic and high-tension electrical concentration, flotation, direct reduction and chemical extraction. Concentration of a number of low-grade siliceous iron ores by the extraction of silica in sodium hydroxide solutions has been reported by the writer and others in the literature.1,2,3,4 Residual concentrates containing as much as 65% iron have been obtained from taconites containing less than 30%. Currently an alternative approach is under study, namely the dissolution of iron oxides from siliceous gangue by extraction in acid, with subsequent recovery of the iron from solution. Such a process for extracting iron oxide from the low-grade oclitic deposits of Alberta with hydrochloric acid was investigated and described by Gravenor, Govett and Rigg.5 The current investigation, which is entirely devoted to extraction with sulfuric acid, is the subject of this paper. In part, the objective of this research was to determine the possibility of leaching iron ores in situ with sulfuric acid. The investigation of a recovery method is left to later research. The ores investigated contained hematite (Fe2O3) as the principal iron-bearing mineral and minor amounts of goethite (Fe2O3 .H2O), magnetite (Fe3O4), and iron-bearing silicates. The gangue was essentially quartz occurring as single crystals and microcrystalline aggregates. Detailed description of the ores may be found in the literature.1,2,4,6 A comparison of the specific ores used in this investigation is shown in the partial analyses of Table I. EXPERIMENTAL METHODS All extractions were made at atmospheric pressure using beakers with a mechanical stirrer for those tests run below the boiling point, and Erlenmeyer flasks for those at the boiling point. A thermostatically controlled hot plate was used for heating, and this maintained the mean temperature within the solution to within ±3°F during extraction. The sample of ore for extraction was weighed to + 0.02 g. For tests below the boiling point, the sample was added to the beaker containing the sulfuric acid solution at the desired temperature. For the boiling-point tests, the sample was added to the Erlenmeyer flask followed by distilled water and the

Jan 1, 1968

By H. M. Howe, E. C. Groesbeck

Fig. 1 shows a volute aging break which developed spontaneously in a hardened and tempered steel helmet between 19 and 38 days after it had been tested ballistically. A similar break, shown in Fig. 2, developed spontaneously in a similar helmet about 40 days after the ballistic testing. In this case the rupture occurred abruptly and with a loud report. The path of rupture in this second case, though much the less regular, is the more interesting of the two, in that it is an approximation to two parallel volutes centered at the point of impact of the projectile, just below D. Several weeks later, after the photograph for Fig. 1 was taken, a similar doubling of the volute crack occurred in this helmet, starting from the end of the eyelash crack near A and spreading thence to the left contra-clockwise for about 1/2 in. The negatives from which these pictures are made have not been touched up in any way, save writing the letters on them. In both cases the trajectory of the bullet was normal to the initial surface at the point of impact, and in both the helmet passed the ballistic test without detectable cracking, under a velocity of impact not far below that which usually causes perforation. The initial surface itself was very nearly spherical throughout the region covered by the break.

Jan 1, 1920

ALABAMA Aldrich.-Lloyd, T. W. Ashland.-Downs, F. G. Geary, E. S. Auburn.-Brown, R. L. Bessemer.-Abbott, C. E. Ball, T. L. Ferguson, V. Salmon, H. S. Stuart. Q. W. Birmingham.-Adams, J. H. Aldrich, T. H. Aldrich, T. H., Jr. Allen, A. W. Armstrong, W. D. Ball, E. M. Bonnyman, J. Bush, M. W. Crawford, G. G. Davis, C. B. Ellis. E. E.

Jan 1, 1923

By W. D. Robertson, J. -P. Briant, M. Gell

The distribulion of dislocatiorls genevnted during the propagalion of hydrogen-induced cracks in Fe-Si cryslcrls was studied as a funclion of temperature f-110o lo 243°C) and silicorz conlenl (3.1 and 4.2 pct). It zoas found that the clislocntiotl densily and the size of the plctslic zone increased with increasing tempevalnre and decreasing silicon conlent. Furtheruvzove, there was a correlcrtion in the dislocalion patterns formed around cracks that propagated at different tempevattrt-es in cvyslals of diffevent silicon contents such that a 1 pcl itlcverise in silicon content was equivalent to a lemperaluore redziclion of approximately 120°C. The experimenlal YeSnllS were compaved with the results of an elastic-plastic wodel that relates the size of the pluslic .zone to the cvack length, internal pressure, and yield stress. it was found that the clzunges in the dislocctlion cryrays with lemperature and combosition can be e-kplaincd by the lemperatrnre and composilion dependence of the yield stress. An wmtsual feature of this study was the observation of low -temperature noncrystrrllogruphic cracks. PLASTIC relaxation can occur at the edge of a moving crack by the operation of pre-existing dislocation sources or by the creation of new sources in a region of perfect 1attice.l&apos;2 The amount of relaxation in a given crystal depends on the crack velocity and the temperature, and can determine whether a crack propagates in a brittle or a ductile manner.1-3 Tetelman and Robertson4 observed microcracks m Fe-3 pct Si single crystals that formed on (100) planes by the precipitation of hydrogen gas during electrolytic charging at 23°C. The plastic deformation accompanying crack propagation was observed in the form of dislocation etch pits and an extensive analysis has been made of the size, shape, and crystallography of the dislocation arrays5-7 This paper describes the effect of temperature on the plastic deformation generated around hydrogen-induced cracks in Fe-3.1 pct Si and Fe-4.2 pct Si single crystals. The observations are compared with the results of an elastic-plastic model for yielding around a crack containing an internal pressure. 1) EXPERIMENTAL PROCEDURES The composition of the materials used in this study are given in Table I. Single crystals of alloy A and the 4.2 pct Si alloy were grown by the strain-anneal method; crystals of alloy B and the 5.1 pct Si alloy were cut from an ingot grown from the liquid. he ~ingle-cr~stal metallographic specimens had a Cross section of 0.100 by 0.050 in. with a length of at least 3/8 in. Specimens were annealed for 3 hr at

Jan 1, 1968

By AIME AIME

COUNCIL* PRESIDENT OF THE COUNCIL. JAMES F. KEMP NEW YORK, N. Y.. (Term expires February, 1913.) VICE-PRESIDENTS OF THE COUNCIL. S. B. CHRISTY BERKELEY, CAL. R. V. NORRIS WILKES-BARRE, PA. GARDNER F. WIILLIAMS WASHINGTON, D. C. (Term expires February, 1913.) . KARL EILERS NEW YORK, N. Y. WALDEMAR LINDGREN WASHINGTON, D. C. BENJAMIN B. THAYER NEW YORK, N. Y. (Term expires February, 1914.)

Jul 1, 1912

[NORTH AMERICA UNITED STATES ALABAMA America.-Dyar, 0. C. Anniston.-Klugh, B. 0. Ashland.-Pallister, H. D. Auburn.-*Poor, R. S. Bessemer.-Creveling, J. 0. Lindstrom, W. A. McKenzie, W. 0. Mitchell, F. R. Birmingham.-Abbott, C. E. Aldrich, T. H., Jr. Armstrong, 0. R. Beard, A. H. Benjamin, F. S. Blackburn, E. 0. Blair, A. J. Blair, 0. S. Blair. H. W.]

Jan 1, 1946