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BARBOUR, PERCY E., Deputy Supt., (Captain), New York State Troopers; Captain, 22nd Regiment, N. Y. N. G. BARLING, 1i. B., 1st Lieutenant, Engineer Officers' Reserve Corps. CHAPMAN, R. H., Major, Engineer Officers' Reserve Corps. DUNN, THEODORE S., 1st Lieutenant, Engineer Officers' Reserve Corps. DWIGHT; ARTHUR S., Major, Engineer Officers' Reserve Corps. FORBES, CARROLL R., Captain, Engineer Officers' Reserve Corps. GOODSPEED,. G. E., JR., 1st Lieutenant, Engineer Officers' Reserve Corps.

Jan 7, 1917

By AIME AIME

TWO weeks ago the writer was lunching in the Engineers` Club in New York with a man who has perhaps the widest acquaintance among engineers of anyone in the country a member of another of the Founder engineering societies. "By the way," lie asked. "who have they nominated for your next president."' "Doctor Becket," I told him- "Oh. that's line," he replied, in a heartfelt tone that rang with sincerity. "I have come in contact with him occasionally and he is just the right type.' And that is the way Dr. Frederick M. Becket impresses everybody. The right type. Most Institute members of the western group of hard-rock minors do not know him, but then they meet him in his swing around the circle next year they will not require a long acquaintance to sense his kindly and outstanding personality, to realize that he is a gentleman in the bet meaning o1 that word, a man of wide sympathies and interests.

Jan 1, 1932

By C. C. Harris

This article presents a general equation describing the xYt surface in batch grinding. This equation contains as special cases most of the relationships which have been deduced from kinetic studies. In an earlier paper an analytical solution of the integro-differential equation of batch grinding was proposed1 as a first approximation of the xYt surface.' A more general equation will be presented here, which appears to combine in a single statement many conclusions reached by experiment. A possible underlying mechanism is that the changing product fineness leads to changes in the particle crushing strength and in the probability of encounter with the crushing media.

Jan 1, 1969

Jan 1, 1955

By R. M. Brick, Arthur Phillips, A. J. Smith

A PREVIOUS publication1§ has described the effect of quenching stresses on the lattice parameter values of high-purity aluminum-copper alloys particularly with reference to the solution and precipitation of CuA12. A similar study has been made of the aluminum-rich aluminum-magnesium alloys. Attention has been directed in the present investigation. to the magnitude of the quenching stresses as affected by the specimen size and shape, the number of solute atoms and the quenching rate. The effect of cooling stresses in causing plastic deformation or cracking has been considered in relation to the physical properties of the alloy. On reheating alloys in the two-phase field, the time required for precipitation to occur has been observed in connection with the degree of supersaturation, the rate of diffusion of the solute atoms as a function of the comparative atomic radii, degree of strain, temperature of reheating and grain size. A few qualitative comparisons on the relative effect of these factors have been drawn between the aluminum-copper alloys and the aluminum-magnesium alloys. STRAIN IN SOLID-SOLUTION ALLOYS A 10 per cent magnesium alloy in the form of chill-cast bars was furnished by the Aluminum Company of America through the courtesy of L. W. Kempf. Additional alloys were prepared using aluminum (99.95 per cent Al) and high-grade magnesium. The alloys listed in Table 1 were melted in an Acheson graphite crucible under a flux of fused MgCl2, CaC12, NaCl. Chill-cast rods were sealed under vacuum

Jan 1, 1935

By Earl W. Palmer, Cyril Stanley Smith

A study of the precipitation-hardening of copper steels1 led the authors to investigate malleable iron containing copper, for the low-carbon ferritic matrix in malleable iron should lend itself admirably to precipitation-hardening. It was soon found that in addition to rendering malleable iron susceptible to improvement by precipitation-hardening treatments, copper has another potentially useful effect as an accelerator of graphitization. Brief mention of these effects was given in a general paper by Lorig and one of the present authors2; the present paper gives further details on the graphitization and precipitation-hardening effects only. After the completion of this work a paper by L. Lykkin3 appeared, confirming the authors' conclusions regarding graphitization. Material Used After some preliminary heats had been made in the laboratory to determine the effect of copper, several castings from commercial air-furnace heats were obtained, and data from these alone are given here. Part of the metal was poured directly and part was treated in the ladle with the desired amount of copper before pouring. Green-sand molds were used, each holding two tensile test pieces of the form adopted by the Malleable Iron Research Institute, or two bars for graphitization studies, 5/8 in, in diameter and 9 in. long, fed through two enlarged sections equidistant from the middle and ends of the bars. Risers of suitable size insured sound castings. Tensile tests were made on the castings after commercial mallealleizing and after special heat treatments to be described. The analyses of the white irons are given in Table 1.

Jan 1, 1935

By Cyril Stanley Smith, Earl W. Palmer

A study of the precipitation-hardening of copper steels1 led the authors to investigate malleable iron containing copper, for the low-carbon ferritic matrix in malleable iron should lend itself admirably to precipitation-hardening. It was soon found that in addition to rendering malleable iron susceptible to improvement by precipitation-hardening treatments, copper has another potentially useful effect as an accelerator of graphitization. Brief mention of these effects was given in a general paper by Lorig and one of the present authors2; the present paper gives further details on the graphitization and precipitation-hardening effects only. After the completion of this work a paper by L. Lykkin3 appeared, confirming the authors' conclusions regarding graphitization. Material Used After some preliminary heats had been made in the laboratory to determine the effect of copper, several castings from commercial air-furnace heats were obtained, and data from these alone are given here. Part of the metal was poured directly and part was treated in the ladle with the desired amount of copper before pouring. Green-sand molds were used, each holding two tensile test pieces of the form adopted by the Malleable Iron Research Institute, or two bars for graphitization studies, 5/8 in, in diameter and 9 in. long, fed through two enlarged sections equidistant from the middle and ends of the bars. Risers of suitable size insured sound castings. Tensile tests were made on the castings after commercial mallealleizing and after special heat treatments to be described. The analyses of the white irons are given in Table 1.

Jan 1, 1935

Jan 1, 1930

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best's as deterrirzed by electron-pro be chalq'sis, the slriations roerre fbund to ILUL' no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,' it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations'', to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.' Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1' or without'3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3'11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium'9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.' High-purity bismuth and antimony, both a 6-nine grade by the manufacturer's emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967

By John Dasher, Wilfred L. Freyberger, James H. Pannell, A. M. Gaudin

WHEN beryllium is bombarded by gamma rays under suitable conditions it evolves neutrons. This nuclear reaction, Bes + y + n + Be", [I] is utilized in the process that is described in this paper. The equation, which physicists often abbreviate to Bevy, n)Be" shows that a photon, y, is absorbed by the Be- sotope of beryllium which then emits a neutron, n, leaving Be8 as a residue." It has been determined that the threshold for this reaction is 1.63 mev; that is, gamma rays having an energy less than 1.63 million electron volts do not have enough energy to remove a neutron from the beryllium nucleus. The threshold value for the beryllium (y, n) reaction is lower than that for any other element. The next most sensitive element is heavy hydrogen (deuterium) whose gamma neutron reaction, D2 (-y, n) H1, has a threshold of 2.2 mev. Thus, gamma rays having an intensity between 1.63 and 2.2 mev will evolve neutrons from beryllium and from beryllium only. Nuclear reactions can be considered as occurring between a projectile and a target. The probability of the occurrence of any such encounter can be expressed in terms of the "cross section" of the target nucleus for the projectile and projectile energy. This cross section, then, is the area normal to the path of the projectile controlled by the target for the purpose of the reaction under consideration. Cross sections are usually expressed in barns, in which a barn is lo-" sq cm. The cross section for Eq 1 is very small, even for nuclear reactions, and of the order of 10"3 barns. It is therefore necessary that a high flux of gamma radiation at the appropriate energy be used to obtain an appreciable neutron yield. In view of the nuclear properties of beryllium it seemed that if pieces of beryllium ore on a moving belt were bombarded with an intense beam of gamma rays, those pieces which are rich in beryllium minerals would emit neutrons at a sufficiently high rate to make it possible to detect that emission, and to use it to actuate a mechanical device for removal of the active from the barren particles. The principal economic source of beryllium is the mineral, beryl. Beryl occurs mainly in pegmatites which are characteristically coarse grained. The suitability of mechanical concentration depends upon the size at which the desired mineral can be liber-

Jan 1, 1951

By James H. Pannell, John Dasher, Wilfred L. Freyberger, A. M. Gaudin

WHEN beryllium is bombarded by gamma rays under suitable conditions it evolves neutrons. This nuclear reaction, Bes + y + n + Be", [I] is utilized in the process that is described in this paper. The equation, which physicists often abbreviate to Bevy, n)Be" shows that a photon, y, is absorbed by the Be- sotope of beryllium which then emits a neutron, n, leaving Be8 as a residue." It has been determined that the threshold for this reaction is 1.63 mev; that is, gamma rays having an energy less than 1.63 million electron volts do not have enough energy to remove a neutron from the beryllium nucleus. The threshold value for the beryllium (y, n) reaction is lower than that for any other element. The next most sensitive element is heavy hydrogen (deuterium) whose gamma neutron reaction, D2 (-y, n) H1, has a threshold of 2.2 mev. Thus, gamma rays having an intensity between 1.63 and 2.2 mev will evolve neutrons from beryllium and from beryllium only. Nuclear reactions can be considered as occurring between a projectile and a target. The probability of the occurrence of any such encounter can be expressed in terms of the "cross section" of the target nucleus for the projectile and projectile energy. This cross section, then, is the area normal to the path of the projectile controlled by the target for the purpose of the reaction under consideration. Cross sections are usually expressed in barns, in which a barn is lo-" sq cm. The cross section for Eq 1 is very small, even for nuclear reactions, and of the order of 10"3 barns. It is therefore necessary that a high flux of gamma radiation at the appropriate energy be used to obtain an appreciable neutron yield. In view of the nuclear properties of beryllium it seemed that if pieces of beryllium ore on a moving belt were bombarded with an intense beam of gamma rays, those pieces which are rich in beryllium minerals would emit neutrons at a sufficiently high rate to make it possible to detect that emission, and to use it to actuate a mechanical device for removal of the active from the barren particles. The principal economic source of beryllium is the mineral, beryl. Beryl occurs mainly in pegmatites which are characteristically coarse grained. The suitability of mechanical concentration depends upon the size at which the desired mineral can be liber-

Jan 1, 1951

By P. Greenfield, P. A. Beck

RECENT work by J. Darby, Jr. in this laboratory has shown that the reported vanadium-rich limit of the s phase in the Co-V system at 1200°C is in error. The appearance of a second phase in s actually is restricted to alloys containing over 68 atomic pct V. The error in the original value is due apparently to a reaction that takes place along the numerous cracks in the s specimens between the alloy and the impurities present in the He + 8 pct H atmosphere in the annealing furnace. Such a reaction and the consequent appearance of a second phase can be suppressed if the alloys are sealed under vacuum in Vycor tubing. The new value of 68 atomic pct V for the vana-dium-rich limit of the s phase in the Co-V system effects slightly the s compositions calculated from average values of N, and N,. for various s phases. The standard deviation between experimental mean compositions and those calculated from the assumption that s is characterized by a constant number of 3d + 4s electrons per atom (N,), is slightly reduced from 9.1 to 8.8 pct. The maximum divergence for the V-Mn s phase is reduced from 15.5 to 14 atomic pct. The standard deviation calculated from constant electron vacancy numbers given by N.. = 4.66 (Mo + Cr + V) + 3.2 (Mn) + 2.2(Fe) + 1.71(Co) + 1.6(Ni) is now greatly reduced, as the maximum divergence for this correlation previously occurred in the V-Co system. This maximum divergence is reduced from 7.6 to 2.3 pct, and the standard deviation for all s- phases is reduced from 4.1 to only 2.9 pct. The correlation for electron vacancy numbers given by N. 5.66 (V when with Ni or Co) + 4.88 (V when with Mn or Fe) + 4.66 (Cr + Mn) + 3.3 (Mn) + 2.66 (Fe) + 1.71 (Co) + 0.61 (Ni) is made slightly worse, and the standard deviation increases from 2.8 to 3.9 pct. These changes, however, do not affect the conclusions of the paper.' The deviation between calculated and experimental s compositions is much less for either one of the electron vacancy correlations than for the correlation with the number of 3d + 4s electrons.

Jan 1, 1955

By Y. C. Liu, W. R. Hibbard

An aluminum single crystal cold-rolled from (110) [1121 essentially retains its initial orientation after 99.6 pct reduction in thickness. The orientation of the recrys-tallized grains of this material can be described in terms of crystallographic rotations about principal poles of deformation texture. DURING the study of the recrystallization of a copper single crystal cold-rolled from a (110) [112] initial orientation, the orientation of the re-crystallized grains could be derived by a 30" rotation of the orientation of the cold-rolled matrix about its <111> poles.&apos; The present investigation was undertaken to extend the work done on copper&apos; to an aluminum crystal also cold-rolled from a (110) [112] initial orientation. Experimental Procedure The procedure of this experiment was similar to that reported for copper.&apos; An aluminum (99.998 pct) single crystal rod* 1 % in. in diameter was grown in back-reflection technique.&apos; The specimen (1.20x 1.004x0.6787 in. thick) was then rolled along the [112] direction. The final thickness was 0.0028 in., giving a reduction in thickness of about 99.6 pet. Specimens were cut from the rolled strip with scissors, and approximately in. of disturbed metal was removed with Tucker&apos;s reagent. The rolling edge remained intact. The specimens were sandwiched between two graphite plates and annealed in a lead or lead alloy bath which was electrically heated. Pole figures were constructed using the techniques previously described.&apos; Specimens were electrolytically polished4 and etched with 47 pct HNO8, 50 pct HC1, and 3 pct of 48 pct HF. The electrolytic polishing method and etching reagent employed for aluminum specimens were not entirely satisfactory and the microstruc-tures could not be studied in any detail. Results and Discussion The octahedral pole figure of cold-rolled aluminum strip is plotted in Fig. 1. The <111> poles spread in the transverse direction approximately 8" for the highest intensity areas. The spread in the transverse direction can be related to a rotation about two <110> directions lying in a plane containing the rolling direction and rolling plane normal. The two <110> directions and a scale of rotation for the <111> poles are shown in Fig. 2. The amount of rotation is consistent for three of the four <111> poles, about 35" to 40". The discrepancy for the fourth pole is believed to be due to limitations of the film technique. Alternate inter-

Jan 1, 1956

By G. W. Healy, W. Craft, D. C. Hilty

By means of a theoretical extension of the Cr-C temperature relation in molten chromium steels to low chromium contents and by a correlation of the ratios of chromium to iron in the slag and metal, a method has been developed for estimating the amount of metallic oxidation during the oxidizing period of a chromium steel heat. Application of this method has indicated that due to temperature limitations metallic oxidation may be excessive for very low carbon steels charged with more than a small amount of chromium. IN the melting and refining of chromium steels the oxidation of carbon to a low level is accompanied by the oxidation of chromium and iron in considerable amounts. For the subsequent recovery of chromium and associated iron from the slag, the amounts of metal oxidized must be known for efficient reduction and control of composition. Further, in order to arrive at an accurate understanding of the process, so that chromium-bearing scrap can be used effectively, information is required on the relation between composition of the charge and weight of metal oxidized to reach the desired carbon content. Crafts and Rassbach1 recently developed an empirical relation between chromium, iron, and manganese oxidized per ton of steel charged, and final carbon content and temperature. This relation did not show any dependence on amount of chromium charged. However, it was felt that such a dependence might be present, so a further analysis of the data was undertaken. Cr-C Relation at Low Chromium Levels Crafts and Rassbach&apos;s results were based on temperatures estimated from the Cr-C relation previously established experimentally by Hilty,2 and on a single temperature observation (immersion thermocouple) on a heat made at low temperature from a charge of carbon steel scrap containing only a small amount of residual chromium. The temperatures estimated from the Cr-C relation were for heats charged with chromium-bearing scrap and which contained substantial amounts of chromium (2 to 10 pct) at the end of the oxidizing period. No data, other than that from the low temperature heat just mentioned, were available for the low and intermediate chromium ranges. In order to extend the range in which temperature may be estimated, the Cr-C relation requires further consideration. The Cr-C relation, expressed as suggests that carbon is zero at zero chromium in the bath. This is obviously absurd, because as chromium approaches zero the carbon content must approach the limit established by the Fe-C-O equilibrium. It is evident, therefore, that the Cr-C relation as defined by Eq. 1 is not valid below some minimum chromium content that may vary with temperature. On the other hand, it is probable that any such limiting chromium content is less than 4 pct at 3200°F, since the experimental data from which the Cr-C relation was derived included several observations at that level with no deviation. In any event, it is apparent that further evaluation of the results presented by Crafts and Rassbach is dependent upon a means for estimating the Cr-C temperature relation in the low chromium region. From the observations of Chen and Chipman9 and thermodynamic data given in Basic Open Hearth Steelmaking,4 the following relation can be calculated for melts containing small amounts of chromium and carbon assuming a carbon monoxide pressure of 1 atm: % Cr -21,250 K&apos; = (%C)2; logK1 == —t— +13.88 [2] Moreover, by plotting Eq. 2 for any given temperature on cartesian coordinates, it can be extrapolated graphically to the limiting carbon content at zero chromium for the specified temperature without serious complications. By means of Eq. 2 and its extrapolation, the Cr-C temperature relations originally established experi-

Jan 1, 1954

By Robert D. Pehlke, Robert G. Blossey

The solubility of nitrogen in liquid iron alloys containing chromium and nickel has been measured in the temperature range 1550° to 1700°C at nitrogen pressures to 1 ah. The solubility surface has been determined for the iron corner of the liquid metallic ternary to 21 pct Cr and 11 pct Ni. The nitrogen solubility increases markedly with increasing chromium concentration. The effect of nickel and the bilinear effect of chromium and nickel are less pronounced. The solubility data are presented, and interaction coefficients are determined from them. THE solubility of nitrogen has been determined in liquid Fe-Cr-Ni binary and ternary alloys. The work in this laboratory has been directed toward a relatively limited composition range, that is to 20 pct Cr and 10 pct Ni. Humbert and Elliott1 studied the entire ternary; but their investigation was, understandably, limited in this region. The region considered here is of the greatest commercial interest. Knowledge of the solubility in these alloys is important for accurate control of the nitrogen levels in various stainless alloys. Also, the solution behavior is of theoretical interest because of its deviations from ideal dilute solution rules at moderate chromium levels. The nitrogen solubility in the iron binaries has been reviewed extensively by Pehlke and Elliott,2 particularly with respect to the dilute solution interaction parameters. More recently, there has been some interest in accurate descriptions of solute interactions in non-dilute solutions. Most of the investigators have adopted a power series fit to accommodate any non-linearity of the data. The Taylor series expansion is adopted here, using Scimar&apos;s notation3 for the interaction coefficients. An alternate method, instead of requiring higher-order expansions, is to restrict the range of the composition variables. A planar solubility surface may be fitted to the data and its range of validity determined. If the axes of this region are displaced from the usual origin—the solvent pure iron—a change in standard state is required for the solution reaction. The standard state for nitrogen in iron is commonly taken as the hypothetical 1 wt pct solution of nitrogen in pure iron. However, for an alloy of appreciable solute concentration, e.g., 13 pct Cr or 18 pct Cr-8 pct Ni, it would be convenient to use that base composition as the solvent and redefine the solution reaction in terms of that particular solvent. A brief derivation follows, defining the free energy of solution in an alloy solvent. Following the treatment by Darken and Gurry,4 for a nitrogen pressure of 1 atm: N (pure component) = N (1 wt pct in solvent) [l] AG=RT ln100/ wt pct N in solvent Taking this reaction for an alloy solvent less the same reaction for a pure iron solvent the relation between nitrogen in pure iron and an alloy is: N (1 wt pct in Fe) = N (1 wt pct in alloy) [2] AG = RT[ln(wt pct N in Fe) - ln(wt pct N in alloy)] Adding ½ N2(g) to each side and subtracting N (1 wt pct in Fe) = ½N2(g), the total free energy for solution of nitrogen in an alloy, referred to nitrogen at infinite dilution, is given by: ½N2 (g) = N (wt pct in alloy) L3] AG°3 = -RT ln(wt pct N in alloy )PN =1 atm Interaction parameters have their usual meaning when ?G°/RT is differentiated with respect to the proper composition coordinate. If desired, the dilute alloy treatment may be utilized with the new reference composition as the solvent. This has. indeed, been done by Small and pehlke5 in their analysis of nitrogen solution in liquid 18-8 alloys. The Sieverts&apos; technique was used for this investigation on an apparatus previously described.6 The materials used in this program were: Ferrovac-E iron, 99.95 pct, Crucible Steel Co.: chromium, 99.95 pct, Union Carbide Metals Co.; nickel, 99.9 pct, International Nickel Co. Recrystallized alumina crucibles were used with no evidence of crucible-melt reaction. RESULTS The locations of the ternary compositions investigated are shown in Fig. 1. The data of Turnock7 and small8 have been alluded to in other papers.5&apos;6 There were no departures from Sieverts&apos; law observed for

Jan 1, 1969

By R. G. Ward, D. R. Gaskell

Using the maximum bubble pressure technique, the densities of iron silicates at 1410°C have been measured blowing helium, nitrogen, and argon. By ensuring equilibrium between the melt and the blowing gas with respect to oxygen potential and by minimizing tempcrature cycling of the furnace, iron precipitation in the melt has been prevented. Thus the previously reported effect of blowing-gas composition on the densities of the melts has been eliminated. Consideration of the oxygen densities of the melts gives an indication of the structural changes accompanying composition change. The density-composition relationship of iron oxide-silica melts in contact with solid iron has been the subject of several investigations1-7 and considerable disparities exist among the various results obtained. Of these investigations, all except one5 have employed the maximum bubble pressure method. In the most recently reported of these investigations1 the density-composition relationship obtained blowing nitrogen differed from that obtained blowing argon. The measured densities obtained under nitrogen were greater than those obtained under argon, the difference being a maximum at the pure liquid iron oxide composition and decreasing with increasing silica content. This observation rationalized the disparities existing among the results of the earlier investigations, showing that two lines, one for nitrogen and the other for argon, could be drawn to fit all the earlier results. No explanation for this phenomenon could be offered. Chemical analysis of rapidly quenched samples of melt for dissolved nitrogen, and direct weighing measurements, excluded solution of nitrogen in the melt from being the cause of the increase in density. The range of blowing gases was extended by Ward and Hendersons who measured the density of liquid iron oxide bubbling helium, nitrogen, neon, argon, and krypton. The measured density was found to decrease smoothly with increasing atomic number of the bubbling gas. The work reported here is a continuation of the program initiated by Ward and Sachdev7 to study the densities in multicomponent melts in which the iron oxide-silica system is the solvent. As such it is necessary to explain or eliminate the anomalous densities of iron silicates under different atmospheres, and the present rede termination was carried out towards this end. EXPERIMENTAL The maximum bubble pressure method of density determination was again employed and the experimen- tal apparatus used was essentially the same as that used by Ward and Sachdev.7 A molybdenum-wound resistance furnace heated an ingot iron crucible of internal diameter 1 in. containing a 2-in. depth of melt. The bubbling gas was blown through a 1/4 -in.-diam mild steel tube onto the end of which was welded a 2-in. extension of 1/4 -in.-diam ingot iron rod, drilled out to 5/32 in., and chamfered to an angle of 45 deg. The blowing tube was introduced to the furnace through a sliding seal and its position was controlled by a vertically mounted micrometer screw which allowed the depth of immersion to be determined with an accuracy of ± 0.01 cm. A Pt/Pt-10 pct Rh thermocouple was located below the crucible and temperature control was effected initially by means of an on-off controller and later by a saturable core reactor. The bubble pressure was determined by measurement of a dibutyl phthalate manometer using a cathetometer. PREPARATION OF MATERIALS Iron oxide was produced by melting ferric oxide in an inductively heated iron crucible in air. The liquid was quenched by pouring onto an iron plate. Silica was prepared by dehydrating silicic acid at 650°C for 12 hr. RESULTS Before any measurements of the density of a melt were made, the density of distilled water at room temperature was measured bubbling helium and argon. Both gases gave the density as 1.00 ± 0.01 g per cu cm which showed that the density of the manometric fluid (dibutyl phthalate) was not affected by contact with the blowing gas. With the furnace controlled by an on-off temperature controller an attempt was made to measure the density of pure liquid iron oxide by bubbling argon. The furnace atmosphere gas and bubbling gas were dried over magnesium perchlorate and deoxidized over copper turnings at 600°C. It was found that the pressure required to blow a bubble at a given depth increased slowly with time, and thus it was impossible to obtain a unique value for the density of the melt. Inspection of the blowing tube after removal from the furnace showed that rings of dendritic iron had precipitated from the melt onto the immersed part of the tube. This is shown in Fig. l(a) where the various "steps" correspond to different depths of immersion. The precipitation of iron was considered to be due to one or both of two possible causes: i) The composition of the liquid iron oxide is that of the liquidus at the temperature under consideration and can be expressed by the equilibrium

Jan 1, 1968

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally.&apos; Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan,3 show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used&apos; for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan&apos;s pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision; using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by, the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.5 However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,&apos; has been deduced for these frequencies: [3fB = 9.20•&apos;./V•Vn- (n-1) • (n+2) /8[1]] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts&apos; as the order of the harmonic. As an example, Spedden and Hannan&apos;s published motion picture of, a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsymmetric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat I than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system, of one degree of freedom can be applied: [1E/m[2] fP = 27] Here f, is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: [t~ = 2/f = 7r\/m/E[3]] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson&apos; 1831) [aP = 4 D2.pL•g•h +7rD•y sin a[4]] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, pL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of-the liquid in cm, y the surface tension in dynes per cm and a the supporting angle&apos; or the one required to insure equilibrium, a being smaller than the contact angle ?. Although demonstrated by Poisson, it has not

Jan 1, 1952

By R. I. Jaffee, F. C. Holden, H. R. Ogden

The effects of grain size and shape on alloys of titanium with nitrogen and aluminum have been determined. Increasing a grain size decreases strength and hardness and increases impact resistance. Quenching from the ß field produces subgrain markings delineating a plates in Ti-N alloys but not in Ti-AI alloys. This suggests a precipitation from the high nitrogen alloys. ALPHA titanium alloys are single-phase alloys with the hexagonal-close-packed structure of a titanium. If these alloys are worked and annealed within the a field, equiaxed structures result in which strength is derived from the solid solution of the alloying elements present. Strain hardening can be used to increase further the strength of a titanium alloys. This is the only other mode of strengthening the a type of alloy. Quenching from the ß field has been noted by many investigators to have little effect on the strength of iodide titanium and on commercial titanium. Ti-A1 alloys were found to be little different in hardness, whether annealed in the a field or quenched from the ß field.&apos; These facts illustrate a characteristic of a titanium alloys: they are insensitive to heat treatments from the ß field. Underlying this heat-treatment insensitivity are the facts that the a-ß field is generally narrow in a titanium alloys, the transformation-temperature range increases with a-stabilizing content, and the a solubilities of the alloying elements are greater than the ß solubilities. When quenching is done from the ß field, there is no supersaturation of the alloying elements in the acicular transformation structure produced. Welds in a titanium alloys generally are ductile, because no transformation hardening occurs during cooling.1,2 Other desirable features of a alloys are: no thermal-stability problem, excellent toughness, and retention of strength at elevated temperatures better than a-ß or ß alloys of comparable room-temperature strength. The prime factors governing the properties of a titanium alloys are the amount and kind of solute present. This can change the a phase from a soft, tough material into a hard, brittle material with no apparent change in microstructure. Moreover, brit-tleness can exist over a wider alloy-content range, without change of phase, than in most other metals. The solutes for a titanium may be divided into interstitial and substitutional types. Oxygen and nitrogen dissolve interstitially in rather large amounts, extending well through the brittle range, and the transformation-temverature ranges are raised in the process.:&apos; , carbon has a maximum interstitial solubility of about 0.5 pct at the peritectoid temperature, while at lower temperatures the solubility decreases to about 0.2 pct.3,5 Substitutional a solutes include aluminum and tin. Aluminum has a high a solubility of 25 pct Al, and increases the transformation-temperature range markedly.6,7 Tin has a high a solubility of about 20 pct, but has a relatively innocuous effect on the transformation-temperature range.&apos; The choice between interstitial and substitutional solutes generally has been conceded to the substitutional solutes because of a belief that they do not have as adverse an effect on ductility and notch toughness. However, a recent investigation8 on the effect of hydrogen on titanium has shown that this element, which is not under compositional control, has a powerful detrimental effect on notch toughness. Hydrogen was shown to form a hydride which is practically insoluble (about 0.002 pct) in a titanium at room temperature, although the solubility at the eutectoid temperature of about 300°C is relatively high, about 0.16 pct. Limited data were presented on the effect of hydrogen on a alloys, where the same impairment of toughness as in unalloyed titanium is found. The work reported here describes the effects of interstitial and substitutional solutes on 1—the mechanical properties of high purity titanium free of titanium hydride and 2—the influence of structural variables on these properties. Nitrogen was selected as an example of an interstitial solute with high solubility and aluminum as a substitutional solute with high solubility. All compositions were well within the ductile range, since it was not intended to study the brittleness problem here, but to study only the factors influencing optimum mechanical properties. Procedures The alloys were prepared from iodide titanium as 1/2 Ib ingots double melted to insure homogeneity.

Jan 1, 1955

By G. Venturello, C. Antonione, G. Della Gatta

Results from work on the effect of inferstitials on recovery and recrystallization of&apos; very pure iron (99.995 pet) doped with nilrogen up to 400 ppm are reported. Nitrided specimens were obtained by heating the iron in a static atmosphere of NH3 + H2. The samples were cold-rolled 80 pet, subjected to a series of isochronal and isothermal anneals, and submitted to examination by X-rays, micrographs, and hardness tests. Small additions of nitrogen show a strong effect in reducing recovery of&apos; the mechanical properties of high-purity iron. At the temperatures of. the experiments, this effect proved greater than in the case of carbon. At 400°C pure iron recovers more than 50 pet of the total hardness increase, carburized iron vecovers 25 pet, and nitrided iron only 10 pet. On the other hand. the addition of nitrogen has, similarly to carbon, a very small effect on recrystallization; the effect is, however, slightly higher than that of carbon. When the concentration Of nitrogen is above the solubility limit in a iron at the temperattue of the experiments, an increase in the frequency of nu -cleation is also observed. THE object of the present work is to improve knowledge on the effect of interstitials both on recovery and on primary recrystallization of pure iron. In fact. at present there are no available data on the effect of nitrogen on high-purity iron. The only work which at present can be somewhat related to this problem is a work of Leak et al.1 in which grain boundary internal friction at high temperature in the presence of increasing amounts of nitrogen is studied by a torsion pendulum. The present work is a continuation of a previous one2 on the effects of carbon. EXPERIMENTAL PART Preparation of the Material. Pure iron was prepared following the same methods used in the pre- vious work2 and was nitrided using controlled quantities of ammonia in an apparatus similar to that used for carburizing. The apparatus consists essentially of a gas-tight quartz tube containing the specimens. The tube, maintained at constant pressure by means of a mercury seal, is placed in a resistance furnace. For nitriding, the NH3 + H2 atmosphere with a suitable concentration of NH3 was introduced into the tube, which had been previously carefully evacuated and degassed by heating at 600°C. The hydrogen used was carefully purified by passing it through a palladium filter. The ammonia required was prepared with the following reaction: CaO + 2NH4CI —CaCl2 + H2O + 2NH3 by heating the mixture of CaO and NH4C1 in a glass flask and then collecting the ammonia in a graduated Hempel burette. For each nitriding program a given amount of NH3 prepared by this method was introduced together with the H2 into the tube previously evacuated. Nitriding of the sample was then performed at 570°C for 48 hr. After this, to ensure a homogeneous distribution of nitrogen, the samples were further heated for 72 hr at 800°C. With this method which uses a static nitriding atmosphere, carefully controlled conditions of purity are obtained. Contrarily, with the conventional continuous-flow methods, using large quantities of circulating gas, there is a greater risk of introducing impurities into the samples. Furthermore, the required nitrogen concentration in the specimen is easily predetermined and obtained. A plot of the relation observed between the initial concentration of NH3 in the gas and the quantity of nitrogen introduced into the iron samples is given in Fig. 1. The data refer to samples of 1.2-mm thickness and to the nitriding conditions previously described. Furthermore, as a comparison, the data relative to two 0.5-mm-thick samples are reported. The presence of a reservoir in the cold zone of the reaction bulb made possible the gradual dissociation of ammonia on the sample in the hot zone. Internal-friction methods were used to determine the content of nitrogen dissolved in the iron samples. Some analyses were also carried out with chemical methods. The following table, Table I, shows a comparison of data obtained with chemical and internal-friction methods. The correspondence between chemical methods and internal-friction

Jan 1, 1964

By J. Szekely

The paper discusses simultaneous heat conduction and diffusion. These problems may arise in slag-metal kinetics and in connection with rapid heating or cooling of specimens. A mathematical formulation is given and it is shown that the transients due to either the variability of the diffusion coefficient with temperature, or thermal diffusion, are unlikely to be important for molten or solid metals and slags. The negligibility of these effects is due to the large values of the ratio thermal diffu-sivity/molecular diffusivity. In many problems relating to transport-controlled metallurgical kinetics the diffusion process is accompanied by the transfer of heat; large-scale metal refining or metal reduction may be quoted as examples. It has been shown that due to turbulent mixing in these systems the relevant transport phe- nomena are best described in terms of "surface renewal models" which require the solution of the unsteady-state diffusion equation.1-1 Problems involving simultaneous diffusion and heat conduction are also encountered in the laboratory in connection with rapid heating or cooling of specimens. The effect of variable temperature on diffusion may be twofold: a) in the absence of "cross effects" the problem, due to variable temperature, is that of diffusion with a variable diffusion coefficient; b) if the Soret Effect is nonzero, thermal diffusion must also be taken into account in the formulation. Although information is available on thermal-diffusion transients in a steady-temperature gradient,4&apos;5 little work has been done on the effect of unsteady temperatures on either the diffusion coefficient or on thermal diffusion.&apos; In the following a formulation is given and solutions presented with a view of examining the areas where these effects may be important.

Jan 1, 1965