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By H. F. Bishop, F. A. Brandt, W. S. Pellini

M. S. Fisher and D. R. F. West (Imperial College of Science and Technology, London, England)—It may be of value to compare certain features of the results recorded in this very interesting paper with those of an investigation11 involving determinations of temperature gradients and rates of solidification of steel blocks of 3 in. sq section, cast horizontally in sand molds, some of which contained chills. Castings in plain carbon steels containing up to 0.8 pct C were made and, throughout this range of compositions, both inverse-rate and direct cooling curves, obtained from thermocouples placed within the mold cavity, showed a major arrest, the temperature of which was taken as the "effective liquidus" for the particular steel in question, solidifying under the conditions of the investigation. At the completion of the arrest, the curves showed a comparatively rapid de- crease in temperature. Some of the steels investigated lay within the peritectic region, and a second arrest at 1485°C was detected. In Fig. 15, which shows the effective liquidus temperatures, the limit of the 8 + liquid field has been placed at approximately 0.5 pct C. In inverse-rate curves corresponding to the thermal center of each casting, there was always a discontinuity, viz: an abrupt change of slope, at a temperature about 10 to 20°C below the "liquidus arrest," after which there seemed to be no significant irregularity in the rate of cooling. Curves corresponding to other positions in the casting generally showed some irregularities below the main arrest, probably as a result of heat flow from the solidifying interior. Even the reproducible discontinuity in the curves for the central positions appeared to have no theoretical or practical significance, though it probably corresponded to a stage in the solidification process at which only a relatively small amount of interdendritic liquid remained. Its temperature, rela-

Jan 1, 1953

By J. F. Enrietto

Internal friction measurements were used to determine the effect of manganese on the solubility and precipitation kinetics of nitrogen. Manganese, in concentrations up to 0.75 pct, has little effect on the solubility at temperatures above 250°C. On the other hand, at Concentrations as low as 0.15 pct, manganese inhibits the formation of iron nitrides, especially Fe4N, even though it may not form a precipitnte itself. The precipitation and solubility of carbides and nitrides have been extensively investigated in the pure Fe-C and Fe-N systems.1-3 In recent years, some effort has been ispent in studying the influence of substitutional alloying elements on the behavior of carbon and nitrogen in ferrite.4 -7 In particular Fast, Dijkstra, and Sladek have investigated the effect of 0.5 pct Mn on the internal friction and hardness during the quench aging of Fe-Mn-N alloys.', ' They found that at low temperatures (below 200°C) the presence of 0.5 pct Mn greatly retarded quench aging. For example, after 66 hr at 200°C very little precipitation had taken place in the iron alloyed with manganese, whereas precipitation was complete after a few minutes in a pure Fe-N alloy. The effect of varying the manganese content and the details of the precipitation process were not mentioned in these papers. Fast' postulated that manganese causes a local lowering of the free energy of the lattice with a resulting segregation of nitrogen atoms to these low energy sites. The segregated nitrogen atoms are bound so tightly to the manganese atoms that they cannot form a precipitate. The internal friction measurements of Dijkstra and Sladek tended to confirm the concept of segregation of nitrogen around manganese atoms, and the increase in free energy on transferring a mole of nitrogen atoms from a segregated to a "normal" lattice site was computed to be - 2800 cal. Dijkstra and Sladek9 distinguished between two types of precipitates: ortho, a nitride of appreciably different manganese content than that of the matrix, and para, a nitride with a manganese content essentially that of the matrix. With each type of precipitate a solubility, again designated ortho or para, can be associated. Since the internal friction maximum in alloys which were aged several hours at 600" C dropped almost to zero, Dijkstra and Sladek9 concluded that the ortho solubility must be very low. The effect of temperature on the ortho and para solubilities has no1: been investigated. There are obviously several gaps in our knowledge concerning the influence of manganese on the behavior of nitrogen in a-iron. It was the purpose of the experiments described in this paper to determine the following: 1) The ortho and para solubilities of nitrogen as a function of temperature. 2) The details of the precipitation process at elevated temperatures. 3) The effect of varying the manganese concentration on the above phenomena. EXPERIMENTAL PROCEDURE Internal friction is conveniently employed in studying the precipitation of nitrides and/or carbides from a -iron because it is one of the few parameters, perhaps the only one, which is not affected by the presence of the precipitate itself. For this reason, internal friction techniques were heavily relied upon in the present experiment. A) Preparat of -. All specimens were prepared from electrolytic iron and electrolytic manganese. Alloys containing 0.15, 0.33, 0.65, and 0.75 wt pct Mn were vacuum melted and cast into 25 lb ingots. After being hot rolled to 3/4 in. bars, the ingots were swaged and drawn to 0.030 in. wires. The wires wen? decarburized and denitrided by annealing at 750° C for 17 hr in flowing hydrogen saturated with warer vapor. To obtain a medium grain size, - 0.1 mm, the wires were then heated to 945oC, allowed to soak for 1 hr, furnace cooled to 750°C, and water quenched. Subsequent internal friction measurements showed that this procedure reduced the nitrogen and carbon concentrations of the alloys to less than 0.001 wt pct. The wires were nitrided by sealing them in pyrex capsules containing anhydrous ammonia and annealing them for 24 hr at 580°C, the nitrogen being retained in solid solution by quenching the capsule into water. Immediately after quenching, the wires were stored in liquid nitrogen to prevent any precipitation of nitrides. By varying the pressure of ammonia in the capsule, it was possible to produce any desired nitrogen concentration. B) Internal Friction. The internal Friction measurements were made on a torsional pendulum of the Ke type,'' a frequency OF 1. or 2 cps being used. For

Jan 1, 1962

By E. C. Truesdale, Gerald Edmunds

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

Jan 1, 1939

By E. C. Truesdale, Gerald Edmunds

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

Jan 1, 1939

By Frank C. Green

Drilling for oil and gas in Missouri in 1935 was mostly confined to proven areas, but was marked by the completion of one of the largest oil wells, 53 bbl., and one of the largest gas wells, 2,000,000 cu. ft., drilled in recent years. A new oil pool, discovered in southern Cass County late in 1934, was further developed; a new pool in southern Platte County is possibly indicated by the completion of a single small well, which flowed naturally; and a deeper sand was developed in the Marota gas pool in Jackson County. Completions dropped to a lower level than in any recent year. A total of 73 wells, which included the deepening of 8 old wells, was drilled. In Bates County, there was one gas well with an open flow of 100,000 cu. ft., and one dry hole. Cass County had six oil wells with about 100 bbl. initial production; one gas well with an open flow of 500,000 cu. ft., and three dry holes. In Jackson County there were seven oil wells with 25 bbl. initial production; 24 gas wells with 7,358,968 cu. ft. open flow, and 27 dry holes. Platte County had one oil well, one small gas well and one dry hole. The oil well flowed naturally about 4 or 5 bbl. per day. It is rather difficult to obtain production figures on either oil or gas leases, but in cases where the figures have been given to the writer in confidence, they disclose conditions comparable with many other regions. One oil lease of 32 acres has produced 125,000 bbl. in four years, or nearly 4000 bbl. per acre. Another lease has made 50,000 bbl., or about 3000 bbl. per acre. It is probable that the total daily production at the end of 1935 was close to 200 hill. per day. A gas pool covering less than one square mile has made 110,111,000 cu. ft. in about 18 months. In this period, the open-flow capacity has been reduced from about 10,500,000 cu. ft. per day to about 3,500,000.

Jan 1, 1936

By Frank C. Green

Drilling for oil and gas in Missouri in 1935 was mostly confined to proven areas, but was marked by the completion of one of the largest oil wells, 53 bbl., and one of the largest gas wells, 2,000,000 cu. ft., drilled in recent years. A new oil pool, discovered in southern Cass County late in 1934, was further developed; a new pool in southern Platte County is possibly indicated by the completion of a single small well, which flowed naturally; and a deeper sand was developed in the Marota gas pool in Jackson County. Completions dropped to a lower level than in any recent year. A total of 73 wells, which included the deepening of 8 old wells, was drilled. In Bates County, there was one gas well with an open flow of 100,000 cu. ft., and one dry hole. Cass County had six oil wells with about 100 bbl. initial production; one gas well with an open flow of 500,000 cu. ft., and three dry holes. In Jackson County there were seven oil wells with 25 bbl. initial production; 24 gas wells with 7,358,968 cu. ft. open flow, and 27 dry holes. Platte County had one oil well, one small gas well and one dry hole. The oil well flowed naturally about 4 or 5 bbl. per day. It is rather difficult to obtain production figures on either oil or gas leases, but in cases where the figures have been given to the writer in confidence, they disclose conditions comparable with many other regions. One oil lease of 32 acres has produced 125,000 bbl. in four years, or nearly 4000 bbl. per acre. Another lease has made 50,000 bbl., or about 3000 bbl. per acre. It is probable that the total daily production at the end of 1935 was close to 200 hill. per day. A gas pool covering less than one square mile has made 110,111,000 cu. ft. in about 18 months. In this period, the open-flow capacity has been reduced from about 10,500,000 cu. ft. per day to about 3,500,000.

Jan 1, 1936

By C. Hertzler

The difference of means of milling characteristics by rock and ore type is tested in a statistical manner in the paper. The null hypothesis being tested is that the sample means of two different populations are equal. It is assumed that the null hypothesis is true when performing the test. Because of this, acceptance of this hypothesis leads to the conclusion that the sample means of the two different populations are equal (or there is no significant difference between the sample means), not that the samples come from the same population, as the author asserts. Rejection of the null hypothesis leads to the conclusion that the sample means of the two different populations are not equal. A P value for this test is reported in Table 2 and is incorrectly identified as the probability that the two samples came from different populations. Actually, what was recorded was 100(1 - p) where p is the usual p-value. The usual p-value measures, on a scale of zero to one, the extent to which the data agree with the null hypothesis. It is the probability of observi" a value of the test statistic (Z score) that is at least as contradictory to the null hypothesis as the one computed from the sample data (McClave and Dietrich 11, 1982). The author makes no mention of the fact that were these tests to be conducted together, the chances of determining that the null hypothesis is not true when it is really true are increased considerably (Snedecor and Cochran, 1980). This is a multiple comparisons problem and should be dealt with accordingly. The usual methods involve adjusting the level of the individual tests. Table 2 reports an incorrect 100(1 - p) value in the comparison of concentrate grades for other rock types with .30 to .69% Cu vs other rock types with .70 + % Cu; 86% should be 98.6%. Although the article can be criticized for poor data presentation and discussion of that data, the point the author makes regarding the use of these statistics in the ore reserve estimation process is well taken. It does not appear that inaccuracies in the statistical interpretations have hindered that usefulness.

Jan 1, 1985

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman&apos;s results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman&apos;s demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman&apos;s experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman&apos;s experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman&apos;s experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman&apos;s Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author&apos;s reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By N. Nakanishi, C. M. Wayman

The effect of small copper additions on the mar-tensitic transformation behavior in Au-47.5 at. pct Cd was studied by measuring electrical resistivity as a function of temperature. The transformation behavior was found to change and transformation start (M,) temperatures for both the ß to ß&apos; and ß to ß&apos; transformations were depressed substantially by the addition of small amounts of copper. Both M, temperatures were lowered approximately 70°C per at. pct Cu. Copper also had the effect of narrowing the transformation hysteresis region (resistivity us temperature), and for the alloy Au-47.5 Cd-1.5 Cu there was little or no hysteresis; in this alloy, the reverse transfmmation upon heating apparently occurs below the thermodynamic equilibrium temperature, To. THE ß phase in the Au-Cd system occurs at the electron/atom ratio 3/2, and is similar to other ß phases in alloys based on copper, silver, or gold. It is of the CsCl type, in which a considerable degree of long-range order persists to the melting temperature.&apos; The phase boundaries of the ß phase are not known precisely below 300° C, but at room tem- perature the phase exists from approximately 46 to 52* at. pct Cd.2 At low temperatures, the ß phase transforms in a diffusionless (martensitic) manner. Alloys having a composition near 47.5 pct Cd transform upon slow cooling to an orthorhombic3 phase, ß&apos;, at - 60°C. Alloys having a composition near 49.0 pct Cd, transform at - 30°C into a phase, ß", which has been recently identified as trigonal.4 Alloys having compositions near 48.5 pct Cd will transform into both the 0&apos; and 0" phases over a range of temperatures. The progress of transformations can be observed

Jan 1, 1963

By C. A. Wert

THE solid solubility of cementite in a-iron has been investigated a number of times and there is now general agreement on the solubility of about 0.018 wt pct at the eutectoid temperature, 720°C. With decreasing temperature, the solubility falls off so rapidly and to such a low value that no data obtained by standard metallurgical methods are available below 500°C. Using a new technique, however, Dijkstral has obtained apparently accurate solubilities down to 400°C; which data agree well with previously measured solubilities in the 600" to 700°C temperature range.&apos; The present paper has in part the purpose of extending his work to still lower temperatures. Earlier work of Low and Gensamer3 on iron has established that the presence of a relatively small amount of carbon can play a tremendous role in affecting the mechanical properties. In particular they found that the yield point remained high as they reduced the amount of carbon in the iron; the yield point dropped only after the carbon content had fallen to something less than 0.003 wt pct, the point where their carbon analysis failed. It seemed desirable to the present author to see if some means could not be found to extend this part of their work. This investigation has then the additional purpose to determine the range of carbon concentration in which the major change occurs. Solubility The method used in the present work to measure small percentages of carbon in a-iron utilizes internal friction. Since this method may not be fa-miliar to the reader, the following explanation will be given (a part of this procedure is from unpublished results of Dijkstra): It is known that the internal friction associated with the diffusion of

Jan 1, 1951

By A. G. Metcalfe, Koeneman

A study of the structure of chemically deposited nickel by Goldenstein, Rostoker, Scpssberger, and Gutzeit has been reported recently. In this work it was shown that the nickel deposit produced by the catalytic nickel-reduction process was an amorphous solid. Crystallization occurred at elevated temperatures when the original powder pattern which showed only a diffuse ring with a d-spacing of 2.01A became sharp, revealing nickel and nickel-phosphide lines. The phosphide was indexed provision%lly on a tetragonal lattice of parameters a = 9.01A and c = 4.42A, which is in reasonable agreement with the structure of Ni3P proposed by No-wotny and Henglein.3 The transformation from the amorphous to the solid state occurs abruptly (e.g., after 7 min holding at 400°C) with the evolution of considerably more than 1000 cal per gm-mole. A more detailed analysis of these effects requires a knowledge of the solubility of phosphorus in nickel. Konstanti-now3 mapped out the phase diagram in 1908 but did not determine the solid solubility. The eutectic was placed at 11 pct P and 880°C. The purity of typical catalytic nickel deposits is very high.&apos; Spectrographic analysis for heavier elements showed only trace amounts of aluminum, calcium, iron, magnesium, lead, and silicon. The term "strace" is a qualitative definition for less than 0.1 pct and probably less than 0.01 pct. Analysis for the interstitial elements yielded 0.04 pct C, 0.0023 pct 0, 0.0005 pct N, and 0.0016 pct H. Some of this material with 7.5 pct P was used in the present work. EXPERIMENTAL METHODS Alloys were prepared from carbonyl-nickel shot and a master composition containing 7.5 pct P. Cold-crucible, nonconsumable-arc melting was used.

Jan 1, 1959

By A. Gemperle

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

Jan 1, 1969

By Nathaniel Herz

The formula very frequently used for computing the economical size of pipe to transmit compressed air is that of D&apos;Arey, as follows: D = cV w1l Where, D = the volume of compressed air delivered in cubic feet per minute, at the final pressure. c = an experimental coefficient determined for the various sizes of pipe, d = the diameter of the pipe in inches. 1 = the length of the pipe in feet. p, = the initial gauge-pressure in pounds per square inch, p2 = the final gauge-preesure in pounds per square inch. w1 = the density of the air, or the weight in pounds per cubic foot at the initial pressure, p1. The most common case is that in which the given quantities are: the quantity of air required, the length of the pipe, and the initial pressure. The method of solution is to assume a pressure-loss and to compute the remaining factor, cd5, thus giving the size of pipe corresponding to the assumed loss of pressure. It is always desirable to try two or more pressure-drops, in order to find the combination that is most satisfactory, since often a small change in the size of pipe will reduce or increase the loss of pressure several pounds. An alternative method is to assume a size of pipe and calculate the corresponding pressure-drop. Each method involves a series of tedious calculations to arrive at the most economical solution, and also requires the use of tables giving the constant, c, the density of the air, w1, and often, for convenience, a table giving the values of the expressions p1-p2 and c J I hare constructed a graphic chart, Fig. 1, for the solution of

Jan 1, 1913

By R. T. Hukki

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

Jan 1, 1955

By L. M. Howe, J. Gordon Parr, E. Saarema

THE decreasing solid solubility limit at the titanium-rich end of the Ti-Cu constitutional diagram,&apos; Fig. 1, suggests the possibility that titanium-rich alloys may be age-hardenable. However, results obtained by Holden et al. reproduced in Fig. 2 show that after quenching from 790°C the age-hardening of an alloy containing 1.7 pet Cu is very slight, while a 0.8 pet alloy decreases in hardness, during heat treatment at 400°C. It was believed possible that powder samples of alloys might show different results from the lump samples used by Holden et al., since small particles are often more sensitive to diffusion processes than larger samples. Consequently, a 1.9 pet (by weight) Cu alloy was made by the technique of levitation melting," checked for homogeneity, and filings of 48-65 Tyler screen size were cut from it for aging experiments. The filings were helium-quenched (by a technique described previously)&apos; from 790°C, sealed in vacuo in silica tubes and aged at temperatures of 400°, 450°, and 500°C. Microscopic and X-ray examinations failed to reveal any structural changes during the aging process. This is not too surprising since early stages of precipitation do not usually manifest themselves in ways that are readily detectable by metallographic methods, and the extent of precipitation on overaging a 1.9 pet alloy is very small. However, hardness readings (taken on a Bergs-man micro hardness tester, using a 25 g load applied to a diamond indenter) do show a hardness peak at each aging temperature, Fig. 3. About a dozen readings were taken on each heat treated sample; the highest reading and the lowest reading were ignored and an average taken of the remaining values. In

Jan 1, 1957

By Lo-Ching Chang, J. Chipman

C. B. POST*—Just what are you showing that has not been shown by fixing the attention on molecular species and choosing the molecular species to give you a perfect solution? J. CHIPMAN (authors&apos; reply)—In general a fairly satisfactory thermody-uamic treatment of slag-metal equilibria can be worked out on the basis of assumed molecular species in the slag. This has been the method used by Shenck and more recently by White. Winkler and I also used it in studying dephosphoriza-tion. Darken and Gurry found that it did not fit satisfactorily in the case of their data on iron oxides. The ionic formulas used here conform to the data much better and probably correspond somewhat more closely with the actual structure of the slags. C. B. POST—It does seem to be similar to you? J. CHIPMAN—It is alternative, and may lead to a more complete understanding. C. B. POST—Have you had a chance to talk to glass technologists on this? Have they been using this type of set-up for glass solutions? J. CHIPMAN—Yes, and the ionic formulas have given them a little better understanding of what liquid glass is like. C. B. POST—Nelson Taylor always said we were going- about slag reactions from the wrong viewpoint when using molecular species. Evidently the glass technologists use ionic species exclusively when dealing with liquid glass reactions. J. CHIPMAN—I agree that it seems more rational and more accurate to use ionic rather than molecular formulas. We should be cautious, however, and not suppose that we really understand the structure of a slag just because we are able to fit its reactions by ionic equations.

Jan 1, 1950

By John Blatchford, William T. Hall

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

Jan 1, 1916

By J. L. Lamon, W. Crafts

Study with the electron microscope of the carbides in vanadium-chromium-molybdenum steels after tempering up to 1000 hr at 600 teelsto 1400°F confirmed that alloy carbides are formed at the secondary hardening temperature by decomposition of the plate-like iron carbides. It was also demonstrated that vanadium carbide persists as much smaller particles than do chromium- or molybdenum-bearing carbides. Conditions conducive to the formation of fine vanadium carbides are indicated to be favorable for high temperature strength. IN order to determine the effects of long exposure at high temperatures on vanadium-bearing steels, a survey has been made of their hardness and carbide structure. The behavior of carbides in the tempering of martensite was studied by X ray diffraction and electron microscope examination of electrolytically extracted residues in greater detail than in an earlier investigation.&apos; A group of steels with about 0.25 pct carbon and containing chromium up to 5 pct, molybdenum up to 1 pct, and vanadium up to 1 pct was either quenched or annealed and then tempered for peri- ods of up to 1000 hr at 600° to 1400°F. Their hardness after tempering agreed with the Hollomon and Jaffe2 relation of equivalency of time and temperature, and with the degree of secondary hardening predicted from composition. Further, the appearance of the carbides indicated that the time and temperature equivalency relation was also applicable to the degree of carbide development. The mechanism of the tempering of martensite was demonstrated more clearly than in the earlier study. It was confirmed that carbides develop from martensite as poorly defined plates of the Fe2C type carbide followed by thickening of the plates with a transition to Fe,C. Finally the plate structure deteriorates into a lacy mass from which alloy carbides emerge as chunky particles that grow slowly with further increase of tempering temperature. Vanadium carbide derived from tempered martensite was found in characteristically small particles that tended to grow very slowly. The addition of chromium or molybdenum to a steel with predominant vanadium carbide tended to introduce carbides of a chromium- or molybdenum-bearing type having a somewhat larger particle size. The Cr,C, type carbide particles were larger than those of the V,C, type and somewhat smaller than the carbides in steel containing both Cr,C and M,C. Similar observations were made of the carbides in the pear lite of annealed steels. It appeared that high temperature properties would be benefited by the retention of the fine carbide particles that result from a balance of composition and heat-treatment designed to produce a maximum amount of vanadium carbide. Procedure: The steels used in the investigation were made with a base of Armco iron in a high-frequency furnace at the Union Carbide and Carbon Research Labs., Inc. The steels were deoxidized

Jan 1, 1951

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who called at Institute headquarters during the period Apr. 10, 1916; to May 10, 1916: Philip P. Baily, New York, N. Y. George W. Otterson Seattle, Wash. John M. Brooks, Jr., Knoxville, Tenn. C. Q. Payne, New York, N. Y. C. A. Burdick, New York, N. Y. Charles F. Potter, Los Angeles, Cal. W. N. Crafts, Oberlin, Ohio. Albert E. Rhoads, Harrisburg, Pa. Andrew B. Crichton, Johnstown, Pa. M. F. Sayre, Schenectady, N. Y. 0. P. Hood, Pittsburgh, Pa. H. V. Smythe, Northpines, Ont., Canada. W. McA. Johnson, Tulsa Okla. W. 0. Snelling, Long Island City, N. Y. G. H. Morgan, New York, N. Y. W. H. Staver, Ophir, Colo. E. G. Norton, Chicago Ill., A. W. Tucker, Salisbury, N. C. M. L. O&apos;Neale, Coal City, Ala. Andrew Weisenburg, Philadelphia, Pa. Arthur H. Brown has resigned his position with the Dome Lake Mining & Milling Co., South Porcupine, Ont., Canada. Robert Sterling has resigned his position as chief engineer of the Goldfield Consolidated Mines Co., Goldfield, Nev., to accept the position of assistant manager of the vanadium mines of the Primos Chemical Co., Vanadium, Colo.

Jan 6, 1916

THE metal iron has physical arid chemical properties which are some- what different from those of steels, but a knowledge of the pure metal is a useful starting point in studying the behavior of steels. Solid iron exists in two different crystalline forms, called alpha (a) and gamma (?) iron the former being the ordinary form at room temperature. When heated above the "A2 point," 769 C (1416 F), the metal becomes nonmagnetic, and at the "A3 point," 911 C (1672 F), it undergoes a change in crystalline form to become gamma iron. 111 the range 769 to 911 C, it is sometimes called beta (ß) iron to distinguish it from the magnetic alpha, but the two are identical in crystal structure. When gamma iron is further heated to 1392 C (2538 F), it changes into delta (d) iron, which is identical with beta or nonmagnetic alpha iron. Pure iron melts (in an inert atmosphere) at 1536 C (2797 F); the melting point is generally lowered by alloys or impurities. PHYSICAL AND THERMAL PROPERTIES OF IRON Many of the properties of iron undergo abrupt changes at the transition temperatures.1 For example, in heating through the A3 point, a sudden shrinkage in volume occurs. Similarly, melting is attended by sharp physical changes such as an increase in volume. Table 16-1 contains a summary of the measured physical properties of pure iron at several temperatures. Usually the properties change smoothly with the range of stability of a given form, but this is not always true. For ex- ample, the specific heat reaches a sharp maximum at the A2 point al- though no transformation occurs. (See Fig. 14-1.) Solvent Powers of Liquid Iron. Liquid iron is capable of dissolving most of the other metals and many nonmetallic elements as well. Of the metals that are liquid at the melting point of iron, only lead, silver, and bismuth refuse to dissolve to an appreciable extent. Table 16-2 contains a list of the common elements classified with respect to their solubility in liquid iron. Those which are very soluble or practically insoluble require no further discussion, but several of the nonmetals that are gases and exhibit limited solubility are of considerable importance to us and merit more detailed consideration.

Jan 1, 1964