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By E. N. Silverman

Mixtures of' MnS, ZFeO-SiO,, ZMnO.SiO, FeO, and MnO were prepared synthetically and used to study the planes ZFeO. Si0,-ZMnO.SiO,-MnS, FeO-MnO-MnS, and Fe0-MnO.Si0,-MnS in the quaternary system. Because the oxides and silicates studied flux MnS, inclusions in this system are partly liquid during rolling. Also, oxygen can modify subsurface inclusions through the reaction MnS + FeO—FeS + MnO during the soaking of ingots and the reheating of blooms and billets. NONMETALLIC inclusions in steel have long been a subject of study and conjecture because the properties of many steels are known to be affected by the the kind and amount of inclusions present. In free-machining steels, the type of inclusion present has a direct bearing on their machinability; in other steels, cleanliness is important and metallurgists direct their efforts at reducing the amount of non-metallic inclusions. Thus, the accumulation of knowledge about the formation and behavior of inclusions during all stages of steelmaking and processing should aid in improving the quality of steels and decreasing the production costs resulting from rejections. Previous studies of inclusions have contributed greatly to our understanding. The investigators have generally examined inclusions in finished steel. Boulger, Moorehead, and Garvey1 found that in Bessemer steels, low silicon contents results in globular sulfide inclusions with attendant high machin- ability ratings. Van vlack2 also found that low silicon contents favor inclusion morphology that contributes to high machinability ratings. Boquist and Stoll* found that silicon content affected sulfide inclusions and machinability of blooms, billets and bars more than did the finishing temperature in the range between 1775° and 2075°F. Carney and Rudolphy3 studied the distribution of sulfur, manganese, silicon, and carbon in a commercial ingot of resulfur-ized steel and found that silicon was concentrated near the bottom. This helped to explain why bottom cuts had poorer machinability. Klinger and Koch4 developed techniques for extracting inclusions from steel, and the technique devised by Gurry, Chris-takos, and stricker5 for extracting carbides can also be adapted to the study of inclusions. A different approach to the study of inclusions in steel consists of synthesizing the constituents that form inclusions and determining the phase eauilibria in the system that contains the constituents. The resulting phase diagrams can then be used to determine the effect of the various constituents upon each other. In this way, it becomes possible to under-

Jan 1, 1962

By R. W. Heckel

The growth and shrinkage rates of second-phase particles of various size distributions are analyzed in terms of five mathematical models. These models apply to various forms of diffusion-controlled growth (one model) and interjace-controlled growth (four models). The expression for diffusion-controlled growth assumes local equilibrium at the interface between the second Phase and the matrix and through the choice of the proper flux area perrnits the definition of minimum diffusion-controlled growth kinetics. The interface-controlled kinetics models consider the situations where the rate-controlling step occurs at either the interlace undergoing solution or the interface undergoing deposition. In addition, each of these interface-controlled kinetics models is analyzed for interface reaction rates which are independent of the thermodynamic activity gradient across the interface or proportional to the gradient. THE variation of the size distribution of second-phase particles in a solute-saturated matrix has been a stimulating topic for many years. Research has been carried out in this area for situations where the matrix was either liquid or solid. It is well-understood that the over-all process results in an increase in the average particle size, a decrease in the total number of particles per unit volume, and a net decrease in surface area. Greenwood1 has presented a mathematical model based upon the mass balance existing between growing and shrinking particles. His analysis is stated in terms of Fick's First Law using concentration gradients set up between particles of different size as a result of the effect of surface curvature on solubility. Greenwood's analysis indicates that the mean particle size should increase approximately as the cube root of time. Asimow2 has shown that several of the simplifying assumptions employed by Greenwood may be eliminated from this diffusion-controlled model with little increase in complexity. Lifshits and Slyozov3-5 have also considered the growth-shrinkage problem involving diffusion-controlled kinetics. Their analysis was extended to include the effects of interacting particles ("kinetic approximation"), particle shape, and elastic strains. These authors also show that the mean particle size varies as the cube root of the reaction time. wagner6 has formulated expressions for both diffusion-controlled kinetics and interface-controlled kinetics in the growth-shrinkage problem. Wagner's diffusion-controlled kinetics is based upon the same form of mass balance using Fick's First Law as used by others and is shown to be applicable to situations where kr >> D (k is the interface reaction constant, r is the particle radius, and D is the diffusion coefficient). This analysis also yields a mean particle size which varies as the cube root of time, in agreement with other workers. Wagner also developed interface-controlled kinetics to handle kr « D. This model was based upon the fact that the interface reaction rate is proportional to the interface area. Wagner assumed that the rate was also proportional to the thermodynamic activity difference, ?a, existing across the interface. Thus, the specific reaction rate at the surface of radius r was defined as k • 4nr2 . ?a. It is the purpose of the present paper to reconsider the processes of diffusion-controlled growth and interface-controlled growth in the variation of particle-size distributions as a function of time at constant second-phase volume. The analyses are formulated in a manner which permits data obtained

Jan 1, 1965

LOCAL SECTIONS (There are 60 Local Sections in the United States, 4 Foreign ) ADIRONDACK Established June 18, 1952 Paul W Allen, Chairman William Webb, Vice-Chairman Edwin Briggs, Secretary-Treasurer National Lead Company Mac Intyre Development Tahawus, New York Paul W Allen, Section Delegate R G Fleck, Alternate Section Delegate

Jan 1, 1954

By B. C. Allen

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

Jan 1, 1970

By S. Shapiro, G. Krauss

The strutural and cr~stallo~aphic features of the plates of austenite produced by the martensite to aus-tenite or reverse martensitic tramformation have been determined in an Fe-33 wt pct Ni alloy. Micro-focus X-ray techniques and single-surface trace analysis 072 bulk samples yielded two distinct habit planes, (0.174, 0.309, 0.~35)~ and (0.375, 0.545, 0.749jM. The former plane uas the one predorninantly observed and its existence was verified by transn~ission electron microscopy. The orientation relation-ship between the reversed austenite and the parent martensite was approximately the same as the Nishiyamna and other relationships reported for the direct tramformation. Replica and thin-joil obser-vations show that both high densities of tangled dis-locations and occasional twins constitute the fine structure of the reversed austenite. Application of the phenomenological theory to a variant of the predominant habit plane defines an irrational plane and direction for the second shear in accordance with the comnplexity of the fine structure. The shear accompanying the reverse martensitic transformation is at least 0.51, the maximnum value of- the tangent oJ the tilt angle measured on surface replicas. A mechanism relating the fine transformation twins in martensite to the nucleation of reversed austenite of the predominant habit is proposed. The reversal of Fe-Ni martensite takes place both at the edges of martensite plates and in a piecewise fashion within them.' The shear-type nature of the reverse transformation is verified by the surface relief which accompanies both edge-type reversal2 and the fragmentation of plates of martensite' as a result of rapid heating above the A, (austenite start temperature). The orientation relationship between the edge-type reversal product and the parent martensite, as determined by transmission electron microscopy, is reported to be within 4 deg of either the Kurdyumov-Sachs or Nishiyama relationships,' but there is no work at present in the literature relating to the crystallography of the platelike reversed austenite. The fine structure of reversed austenite after heating to 50°C above the Af is reported4 to be composed primarily of tangled and jogged dislocations in concentrations up to 10" per sq cm. A replica investigation of partially reversed Fe-Ni martensites5 corroborates the increase in dislocation density following reversal and presents indications of other possible modes of fine structure. This paper reports on an investigation performed to examine in detail the morphology and crystallography of the plates of reversed austenite and the shear which accompanies their formation in a matrix of Fe-Ni martensite. EXPERIMENTAL PROCEDURE Discs of a high-purity Fe-32.9 wt pct Ni single crystal served as the starting material. The single crystal had been produced in the course of an earlier investigation6 and the carbon content was determined at the time to be 0.006 wt pct. The M,, and the A,, were respectively -120" and 300°C. Partial transformation to martensite was performed at -125°C and reversal of some of the martensite was accomplished by heating in the temperature range 340" to 355°C. Most samples were heated to the reversal temperature by immersion' in a salt bath for 2 min. For surface-relief studies some polished and etched Samples were heated in a tube furnace for ten min in a hydrogen atmosphere maintained over the samples throughout the heating and cooling cycles. Samples were prepared for metallographic examination by electropolishing and etching with an HC1-HNOs-H20 et~hant.~ On one of the surface-relief samples two sets of fiducial scratches were placed on the etched sample by drawing it over a slurry of 0.06 p alumina on a "microclothJ'. The orientations of individual plates of martensite were determined by X-ray analysis. A Rigaku-Denki microbeam X-ray generator in conjunction with a Micro-Laue camera with facility for precision location of the sample in front of the beam was employed for this purpose. The collimator size was 30 p and the specimen to film distance was 5 mm. The Laue photograms were enlarged to an equivalent 3-cm specimen to film distance for analysis. The orientation of each of the plates of martensite was compared to that of the parent austenite and the relationship be -tween the two phases was, in all cases, within a few degrees of those predicted for the direct transformation. The orientation relationship between one of the larger plates of reversed austenite and its parent martensite was determined in a similar manner. The habit plane of the islands of reversed austenite in the X-rayed plates of martensite was determined by a single-surface trace analysis. Each reversal island had with the parent phase one comparatively straight boundary which was presumed to represent the habit plane trace. The pole locus technique7 was applied to traces from six different plates of martensite to determine the indices of the habit plane. A 40-cm stereographic net was employed for this analysis The morphology and fine structure of the reversed austenite were studied by electron microscopy of pre-shadowed direct carbon replicas,5 and the macroscopic shear was evaluated by a two-stage replica technique similar to that employed in electron fractog-

Jan 1, 1968

By G. R. Leverant, C. P. Sullivan

Re crystallized TD-nickel mi-2Th0,) in both coated und uncoated conditions was fatigued at 1800°F at total strain ranges varying .from 0.2 to 0.75 pct. The fatigue life of uncoated inaferal, Nf, was related to the total strain range, ?eT, by (2Nf/021AeT = 0.014. A duplex Al-Cr pack coating increased the fatigue life by about a factor of two. The cracks that led to failure in both coated and uncoated material were initiated at the outer surface, indicating that the mechanical properties of the surface layers were important in determining fatigue life. Crack propagation and subsurface crack initiation in the TD-nickel occurred preferentially at grain boundaries with cavitation at thoria particle-matrix interfaces an integral part of the grain boundary fracture process. The importance of both the grain morphology developed during thermome chanical processing of TD-nickel and the distribution of thoria particle sizes to fatigue resistance are discussed. THE fatigue properties of only a few dispersion-strengthened metals have been studied at temperatures 0.5 Tm;1,2 among these have been lead and aluminum containing oxide dispersions. TD-nickel is a material of interest for application in aircraft gas turbine engines, but little fundamental information is available on its behavior under cyclic loading conditions. In this study, the low-cycle fatigue properties of TD-nickel were determined at 1800°F with emphasis on the 101-lowing; 1) the relation of the grain morphology produced during thermomechanical processing to crack initiation and propagation; 2) the role of thoria parti-cles in the fracture process; and 3) the effect of an oxidation resistant coating on fatigue life. I) MATERIAL AND EXPERIMENTAL PROCEDURE The TD-nickel was supplied by DuPont as a 5/8-in. thick plate which had been subjected to a proprietary series of thermomechanical treatments with a final anneal at 2000°F for 1 hr in hydrogen. The composition of the material is given in Table I. At the test temperature of 1800°F, the 0.2 pct offset yield stress was 15,000 psi, and the elongation and reduction in area were 4.6 and 3.0 pct, respectively. The microstructure of this material has been previously described.&apos; Briefly, it consists of an array of lath-shaped grains, about 0.15 mm in thickness, with the long dimension of each grain parallel to the primary working direction, Fig. 1(a). The presence of very small annealing twirls, Fig. l(b ), together with the absence of extensive dislocation networks, Fig. L/C), indicated that the material was in the recrystal- Table I. Composition of TD-Nickel ThO2 2.3 vol pct C 0.0073 wt pct lex 0.01 wt pct Cr 0.01 wt pct Cu 0.004 wt pct S 0.001 wt pct Ti <0.001 wt pct Co <0.01 wt pct Ni bal lized condition. Commercial TD-nickel sheet has a similar grain size and shape, but unlike the present material is not recrystallized as evidenced by the absence of annealing twins and the presence of a well-developed dislocation substructure.4 The plate material had Young&apos;s moduli in the rolling direction of 22 x 106 psi and 13 x 106 psi at room temperature and 1800°F, respectively, indicating a texture with a strong {100}<001> component in agreement with previous observations on recrystallized TD-nickel sheet.596 The 2.3 vol pct of thoria particles were uniformly distributed although some clustering and stringering of larger particles was occasionally seen. The average diameter of the particles was 450 and the calculated mean planar center-to-center spacing was 2100Å. Two specimens were coated with a duplex A1-Cr pack coating. The coating was somewhat nonuniform from one position to another along the gage length. An area of the coating after testing is shown in Fig. 2. Electron microprobe analysis revealed the following zones in the various lettered regions indicated in Fig. 2: A) a bcc matrix of B-NiA1 with some chromium in solid solution along with a fine dispersion of a chromium-rich second phase which was probably precipitated during cooling from the test temperature to room temperature; B) fcc y&apos;-Ni,Al with some chromium in solid solution; C) porosity; D) a two-phase mixture of a chromium-rich solid solution containing nickel and aluminum and a small volume fraction of a nickel-rich solid solution having approximately the same composition as the immediately adjacent portion of region E, E) the TD-nickel substrate containing chromium in solid solution to a depth of 5 to 10 mils. As expected from the nature of the diffusion processes involved,7 the thoria particles were present only up to the layer of porosity, region C, Fig. 2. The measured thickness of the coating proper, zones A to D, after testing was 1 to 2 mils. The specimen design and testing techniques have been previously discussed.&apos; Stressing was axial and parallel to the lath-shaped grains (i.e., parallel to the rolling direction). The total strain range was controlled between zero and a maximum tensile strain varying from 0.2 to 0.75 pct. (The test at 0.2 pct total strain range was switched to load control at 1030 cycles at which point the peak tensile and compres-

Jan 1, 1970

By R. Shuttleworth, R. Smith

A Knudsen effusion tnethod I~as been used lo measure the vapor pressure of pure iron in the temperature range 1000° to 1500°C. Neutron-irradiated , natural iron was used and the Mn&apos;~proclzdced by the (n, p) reaction removed by evaporation at high temperature. The results can be represented by the equation: where pM - 1.088 x 107 atm and T, = 20,890°K. A value of 100.2 kcal per g- atom was obtained for AH;. THE vapor pressure of pure iron in the temperature range 1000" to 1500°C has been measured. Radioactive iron and a Knudsen cell technique were used and the Mn&apos; produced by an (n, p) reaction removed by evaporation at high temperature. From the variation of vapor pressure with temperature values of the enthalpy and entropy of solid iron have been found. Previous workers2 used a Lang-muir method and measurements were made over a smaller temperature range than that in this work. EXPERIMENTAL The apparatus used was similar to that of Pyle and Shuttleworth, and McLellan and Shuttle worth. However, because of the higher temperatures the Knudsen cell was machined from tungsten bar and the flanged furnace tube was beryllia. Heating was by passing a high current (70 amp at 7 v for 1500°K) through a strip of tantalum foil laid across the top of the cell and through a turn of molybdenum wire around the furnace tube. This method of heating ensured that the top of the cell was slightly hotter than the base and prevented condensation and re-evaporation from the orifice. The temperature was measured by means of a pt/Pt 13 pct Rh thermocouple spot-welded to the base of the crucible. To ensure accurate temperature measurement the iron was in the form of a thin disc (0.75 cm diam by 0.075 cm) which lay on the base of the cell. The high-purity iron was irradiated in the Harwell pile for a week at a neutron flux of 1.2 X 10" neutrons per sq cm per sec. The isotopes fe&apos;~ and Fe" are produced by (n! y) reactions but only Fe", half-life 45.1 days, is a emitter; Mn which is also a y emitter, half-life 300 days, is produced simultaneously by an (n,p) reaction.&apos; Immediately after irradiation of natural iron the ratio of ~e" to Mn y activity was 100:l. However, manganese is very much more volatile than iron and almost all the y activity of the condensate is due to Mn&apos;~. Thus it was essential to eliminate all the manganeses before any measurement of the vapor pressure of iron was made and this was done by preliminary heating for 20 hr at 1400°C. For each determination the iron was dissolved from the target with acid and the y activity compared to a known weight of iron. By means of a y-ray spectrometer the y-activity measurements were made at the 1.09-mev peak of the 17e5&apos; spectrum where the background was of the order of 3 cpm. Despite the low specific activity of ~e" a mass of 10- " g of iron could be determined corresponding to a vapor pressure of about l0-&apos;&apos; atm. RESULTS The vapor pressures were calculated from the equation: Where m is the mass of iron effusing in a time t through an orifice of area a2, r is the radius of the target, Z is the distance from the orifice to the

Jan 1, 1965

By F. J. Smit, S. C. Sun

Flotation variables were investigated for the re-clamation of phosphate from a Florida washer slime. Under optimum conditions, 92% of the phosphate was recovered. Further cleaning of the rougher flotation concentrate resulted in a product containing about 30% P2O5 with a phosphate recovery of 65%. The enormous amount of slimes rejected in the Florida pebble phosphate fields, containing roughly one-third of the phosphate in the pebble matrix,1 has long been considered as a serious problem to the industry. The mere disposal of these slimes has posed an almost insurmountable task for several investigators.2-5 Some companies still resort to huge surface dams, some covering 1800 acres, for slime disposal.6 Information on the recovery of fine phosphate from these slimes is scanty. Dry separation8 and electrostatic beneficiation8 were suggested, but would necessitate radical changes in the present mining and concentration methods. Haseman10 proposed the selective flocculation of colloidal phosphate with starch, while Ralston11 suggested the removal of clay from the matrix by amine flotation. Leaching of the slimes for recovering the small amount of uranium was attempted by the Battelle Memorial Institute12,13 but proved to be economically unfeasible. The purpose of the present investigation was to determine the optimum fatty-acid flotation conditions for reclaiming the phosphate discarded with the Bartow washer slime. Prior to the flotation experimerits, however, the size distribution and the minera-logical composition of the employed slime had to be determined.

Jan 1, 1963

PRESIDENT Michael Lawrence Haider New York City PAST PRESIDENT Willis McGerald Peirce New York City VICE-PRESIDENTS 0. B. J. Fraser, New York City J. B. Morrow, Pittsburgh, Pa. J. L Gillson, Wilmington, Del. &apos; L F. Reinartz, Middletown, 0. Philip Kraft, New York City R. W. Thomas, Tucson, Ariz

Jan 1, 1952

By Arthur Tauber, Horst Kedesdy

FERRITES are sintered metallic oxides of the spinel structure type1 and belong to the class of soft ferromagnetic materials. Similar to a ceramic, they can be formed and fired to a dense body, exhibiting a high electrical volume resistivity ranging from 102 to 102 ohm-cm as compared with 10-6 ohmcm for some of the metallic magnetic materials. This high resistivity, with resulting low eddy current losses, finds special application at high frequencies. The dispersive susceptibility of ferrites at microwave frequencies has also led to many applications in this field. Where high resistivity with high permeability is desirable, ferrites are used in low frequency applications. During the last few years ferrites exhibiting rectangular hysteresis loops have been developed for computer and magnetic memory systems. The general formula for ferrites is MeFe2O4 where Me is a divalent metal ion such as Ni, Zn, Mg, Mn, Cu, Cd, and Fe. Only two of these ferrites are nonferromagnetic, namely, those with Zn and Cd. Solid solutions can be formed between different ferrites, and it is of interest to note that solid solutions of a ferromagnetic ferrite with a nonferromagnetic ferrite yield much better magnetic materials than the basic ferrite body. In general, it can be said that the solid solution formation between ferrites has widened the field of ferrite synthesis and has led to methods of preparing materials with a large variety of magnetic properties.

Jan 7, 1957

By J. K. Abraham

In recent years there has been interest displayed in the precipitation phenomena occurring in austenitic alloys based on the binary Fe-Ni system.1&apos;2 Previous communications have been extended covering the kinetics of clustering in the Fe-Ni-Ti system and the effect of cluster size on subsequent mechanical properties.3&apos;4 To a great extent the question of coherency, which has a dominant role in determining the mechanical properties, is dictated by the degree of misfit between the precipitate and matrix. Thus, the change in lattice parameter of the matrix with composition is an important variable that should be examined. The lattice parameter, ao, of austenite was determined for Fe-29.75 Ni-1 to 6 Ti and Fe-27 Ni-1 to 10 Ti alloys in this study. The alloys used in this investigation were melted in a vacuum induction furnace from a starting stock of plast iron (99.95), electrolytic nickel (99.9), and ti- tanium sheet (99.5) in a MgO crucible. The alloy compositions in atomic percent are given in Table I and their relative position in the Fe-Ni-Ti ternary is indicated in Fig. 1. The chemical analyses were taken from the homogenized bulk materials treated in a manner related earlier.3 A diamond file was used to obtain powder from the bulk. To remove the stresses induced by filing, the powders were austenitized at 1875°F for

Jan 1, 1969

By E. A. Devuyst, M. A. Mosoiu, V. A. Ettel

Nickelic hydroxide is an important metallurgical reagent used for precipitating cobalt from nickel sulfate solutions. Existing methods of preparation of nickelic hydroxide involve electrolytic oxidation of Ni(OH)2 or the use of strong oxidizing agents such as chlorine, ozone and persulfate. Although the oxidizing properties of the SO2 + O2 system have been known for some time, e.g., detection of SO2 and oxidation on iron in acidic solution, the application of this system for the preparation of nickelic hydroxide as a process was not considered in the past. The present paper describes a new method for chemical preparation of nickelic hydroxide which has been developed in INCO laboratories. The technique consists of reacting nickelous hydroxide suspensions with a slurry of calcium sulfite in the presence of air or oxygen. The main advantage of the process is the cost of reagents and an absence of soluble by-products (e.g., C1-). The chemistry of this process is unusual since the redox potential obtained during the reaction exceeds that of the oxygen electrode. Therefore, the effect of CaS03 is not just a catalytic acceleration of the reaction NI(OH)~ + 02. The so3= must be involved in the stoichiometry of the overall reaction producing in the initla1 phase some strongly oxidizing intermediate species.

Jan 1, 1981

By N. D. Policow, J. S. Orphanos

Dewatering fine clean coal fractions, -595µm (-28 mesh), represents one of the most difficult and costly separations in typical plant circuits. Since 1969, the screen bowl centrifuge has offered an economical alternative to filtration/thermal dyer combinations. The performance of screen bowl centrifuges has been continuously modified and improved to dewater not only coarser coals, but also today&apos;s variety of ultrafine material. Test comparisons with alternative methods show the screen bowl centrifuge to be most cost effective and efficient when all factors are considered.

Jan 1, 1984

By S. A. Ford

I would like to call the attention of our Bessemer steel manufacturers to a few facts in regard to the action of the manganese in the spiegel with the oxide of iron in the blown iron. The oxygen is united with the iron as a magnetic oxide, as Gautier asserts, and this oxide is reduced to a protoxide by one atom of the manganese uniting with one atom of the oxygen of the magnetic oxide of iron. This oxide of manganese and the protoxide of iron thus formed unite with the silica which has been formed by the oxidation of the silicon in the pig iron. Mr. Snelus and others

Jan 1, 1881

By R. G. Davies

The activation energy for steady state creep above -500°C is observed to be independent of the applied stress although it varies from -67 kcal per mole at 2 at. pct Si to -100 kcal per mole at 11 at. pct Si due to changes in crystallographic order. The magnitude of the activation energy, by comparison with Fe-A1 alloys, indicates FeSi type of order in certain alloys. X-ray results confirmed the presence of FeSi type of order. It is proposed that dislocation climb is the rate controlling mechanism for all the alloys. It has been demonstrated that when a diffusion mechanism is the rate controlling process, the formation of a superlattice in brass,1 Fe3A1,2 Ni3Fe,3-5 and Feco6 1) increases the creep resistance, and 2) increases the activation energy for steady state creep. Furthermore, a study of creep in Fe-15 to 20 at. pct A1 alloys7 has revealed that as the alloy composition approaches the long-range order field, there is an increase in the activation energy for steady state creep which is thought to be due to an increase in short range order. Fe-A1 and Fe-Si alloys are similar in that they both form the DO3 superlattice in which aluminum or silicon atoms have only iron atoms as first and second nearest neighbors. There are, however, two important differences between the alloy systems: 1) The superlattice formation at -350°C commences at -10 at. pct si8 as compared to -20 at. pct Al,9 and 2) Fe-A1 alloys form a FeAl (B2 type) super-lattice where aluminum atoms have all iron first nearest neighbors even at 22 at. pct Al, but so far no similar FeSi superlattice has been observed. With the similarity between Fe-A1 and Fe-Si alloys in mind, alloys of iron with 2 to 11 at. pct Si were examined for variations with composition of the activation energy for steady state creep and of creep strength. The temperature range of greatest interest was above 1/2 TM (TM is the absolute melting temperature) where it is usually observed that diffusion is the rate controlling process. A subsidiary X-ray investigation of the Fe-Si system was undertaken in an attempt to define the position of the order-disorder boundary as a function of cooling rate. EXPERIMENTAL DETAILS a) Creep. Specimens whose gage length was 1.5 in. and with a cross-section 0.04 by 0.08 in. were strained in tension by a lever-arm arrangement, and the load was adjusted between each creep test to maintain constant stress. The apparatus and mode of operation have been fully described in a previous publication.7 As each test produced a creep strain of 0.25 pct, the variation in stress during the test was negligible. Creep strain was measured at the end of one of the alloy steel grips by a displacement transducer with the out-of-balance potential being recorded on a variable speed recorder. The full-scale deflection of the recorder could be varied in steps to give limits of sensitivity of between 0.1 and 0.001 pct creep strain. The alloys, Table I, were made available by the Metallurgical Department, National Physical Laboratory (N.P.L.), england,10 and by the Research Department, General Electric Co. (G.E.), Schenectady, N.Y. They were hot worked at -850°C, warm worked at 550° to 650°C, and recrystallized in vacuum at -750°C to give a grain diameter of -0.1 mm. All the alloys had a very low impurity content; those from the N.P.L., for which a complete analysis is available,&apos;&apos; show carbon less than 0.026 pct, manganese less than 0.006 pct, and oxygen plus nitrogen less than 0.0024 pct. b) X-ray Procedure. A General Electric XRD-5 X-ray set with a focussing lithium fluoride mono-chromator in the diffracted beam, and a pulse height analyzer to eliminate harmonic wavelengths of the cobalt radiation, was used to investigate the structure of several very fine grained (grain diameter <.01 mm) Fe-Si alloys after the following heat treatments: 1) Quenched from 700°C, 2) slow cooled from 650°C (-40°C per hr), and 3) very slowly cooled from 400° to 100°C (10°C per hr with a 24 hr anneal every 100°C). The method of obtaining the diffraction pattern over the range of 20 from 15 to 45 deg was to count for at least 100 sec every l/3 deg with a slit subtending 1 deg in 20 at the focus; the probable counting error was less than 2 pct.

Jan 1, 1963

By David T. Peterson

Calcium metal was found to deoxidize thorizcm at 1000° to 1200° C. The reaction kinetics were determilled and related to the diffusion coefficients of oxygen in thorium. The solubility of oxygen in thorium, the minimum oxygen concentration, and the diffusion coefficient were determined from 1000° to 1200°C. This firocess results in the lowest oxygen concentrations zohich have been reported for thorium metal. FOR many years it has been known that calcium metal will reduce thorium oxide to thorium metal. This reaction has been the basis for several methods of preparing thorium metal. From the equations giv-by Kubaschewski and vans, &apos; AF" for the reaction Cao, + Tho,(,) - CaO(,, + Th(,) was calculated and found to be -3.4 kcal at 1000°C, -2.5 kcal at llOO°C, and -2.0 kcal at 1200°c. Thorium is very slightly soluble in liquid calcium, and the solubility of calcium in solid thorium is very low. Consequently these metals would be in essentially their reference states. If thorium containing oxygen were equilibrated with liquid calcium between 1000° and 1200°C, the oxygen content of the thorium would have to be below the solubility limit in thorium. Oxygen is one of the impurities most difficult to remove from thorium and is the most abundant impurity in metal prepared by almost all known methods. Fortunately, oxygen does not have a large influence on the properties of thorium because the solubility in solid thorium is very low. EvenT in thorium containing 100 ppm of 0, particles of thorium oxide can be observed in the microstructure. In view of the incompatibility of thorium oxide and liquid calcium and the low solubility of thorium oxide in thorium, the deoxidation of thorium by this method was investigated. For thorium containing an amount of oxygen well in excess of the solubility limit, the reaction should proceed in the following sequence. The oxygen content of the thorium matrix near the surface would be depleted by the diffusion of oxygen to the surface. At the surface, the oxygen would react with calcium to form calcium oxide. To maintain equilibrium within the thorium, thorium oxide would dissolve to keep the matrix saturated. Consequently, the thorium-oxide particles would disappear first at the surface and then the particle-free rim would grow in thickness. If the rate-controlling step were the diffusion of oxygen through this layer of thorium which was growing in thickness in direct proportion to the amount of oxygen removed, the well known parabolic time law should be observed. If the oxygen concentration at the surface of the thorium and at the inner surface of the deoxidized rim were known, the diffusion coefficient of oxygen in thorium could be calculated from the parabolic rate constant. EXPERIMENTAL PROCEDURE The thorium metal used in this study was prepared by calcium reduction of ThF, by the method described by Wilhelm.&apos; The analysis of this metal is given in Table I. The carbon was determined by combustion, the oxygen by the HC1-insoluble residue method, nitrogen by the Kjeldahl method, and the other elements by emission spectroscopy. A section of this ingot was hot rolled at 600°C to 1/4 and 1/8-in. thick plates. Specimens approximately 7/8 in. square were cut from these plates, and all surfaces of the specimens were cleaned and smoothed by filing with a clean file. Individual specimens were placed in 1-in. diam by 2-in.-long tantalum capsules. Approximately 1 g of clean, high-purity calcium was placed in the capsules and an end closure arc-welded in place. The tantalum capsules were sealed in Inconel crucibles to protect the reactive metals from oxidation. The entire loading procedure was done in a glove box filled with pure argon. The loaded crucibles were placed in a muffle furnace, controlled within 2OC of the desired temperature, for a measured length of time. After the specimen had cooled to room temperature, it was sectioned perpendicular to the large faces and through the mid-point of two of the sides. The sectioned specimen was mounted and polished through Linde A abrasive. The rim which was free of thorium-oxide particles could be clearly observed microscopically as mechanically polished. Twenty measurements of the thickness of the rim were made at equally spaced points far enough from the end of the

Jan 1, 1962

By A. G. Crocker

The positions of twin reflections in electron-dijjcraction patterns obtained from thin metal foils may he calculated for any twin in any crystal structure by means of an elementary application of vector algebra, General equations for the four classical orientation relationships are presented using the superscript and subscript notation of the tensor calculus, which is briefly described. As an example of the application of these expressions, the case of twinned rhomhohedral crystals, and hence as a special cased twinned cubic crystals, is examined. CONSIDERABLE interest has recently been shown in the interpretation of electron-diffraction patterns obtained from twinned regions of thin metal foils. In the present paper, it is shown that the necessary information may be obtained directly for all twins in any crystal structure by means of a very elementary application of vector algebra. The equations involved are most conveniently presented by making use of the very powerful superscript and subscript notation of the tensor calculus. The use of this notation will first be described and then applied to the problem of calculating diffraction patterns for any twinned crystal. Finally, as an example of the application of the method, the specific case of twinned rhombohedra1 crystals will be considered.

Jan 1, 1965

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.&apos; DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature&apos; giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.&apos; If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

C. H. MATHEWSON, Chairman SAM TOUR, Past-chairman W. A. SCHEUCH, Vice-chairman T. S. FULLER, Vice-chairman W. M. CORSE, Secretary-Treasurer 810 Eighteenth St., N. W. Washington, D. C. Executive Committee J. L. CHRISTIE ARTHUR PHILLIPS E. H. Dix, JR. GUY C. RIDDELL W. M. PRIRCE J. WALTER SCOTT&apos; A. J. PHILLIPS&apos; H. M. WILLIAMS EL M. WISE

Jan 1, 1932

By F. R. Archibald, C. M. Nicholson

The present paper may be considered complementary to an earlier contribution on the same subject by F. R. Archibald and C. F. Jackson.1 It is particularly concerned with engineering and technological aspects of the operations at the Harleyville Alumina Plant during its period of operation from January 1945 to July 1946. The plant was built for and operated by Ancor Corporation, at Harleyville, South Carolina, as part of the government sponsored wartime program related to alumina production from domestic raw materials. The main purpose of the program was to secure technical and engineering data, based on actual plant experience, that might serve as a foundation for large scale production of alumina from raw materials other than bauxite. The Harleyville plant was directed specifically to treatment of clays found in very extensive deposits in the Carolinas and Georgia using the lime-sinter process developed by Ancor Corporation. It is considered that the purpose stated above has been served and this paper is to record and discuss some of the more important findings. The main factor in location of the plant at Harleyville was the presence in that locality of a rather remarkable deposit of high calcium limestone. The clay mining operation was centered near Aiken, S. C., and although a rail haul of ninety miles was involved there were, at the time, factors favorable to the Harleyville location offsetting, in part, the cost of transportation of clay, There are, no doubt, locations in the general area where clay and limestone deposits may be found in closer proximity hut they had not been proven up when the project was undertaken. Availability of power from the Santee-Copper development whose high tension line skirted the Property; ready access to rail and highway transportation; the promise, realized in actuality, of ample supply of soft water; and availability of labor supply were other factors of importance. Moreover, the general area has the decided advantage, for this type of operation, of a mild climate. Construction was begun in August 1943, and although stopped for a time priding review of the general situation that fall, it was resumed, albeit with less urgency, and substantially completed by the end of 1944. The total capital cost was approximately $3,460,000 The first alumina was turned out in April 1945 and from then until the plant was closed down in July 1946, the operations followed a succession of periods of production alternating with periods in which minor alterations were made in conformity with experience. Steady improvement was made and at the time Operations were discontinued it was considered that experience and the necessary engineering were in shape for removal of the remaining bottlenecks and a somewhat major revision in one section of the plant. Unfortunately this could not be carried out and it was necessary to discontinue the

Jan 1, 1949