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By R. E. Smallman

R. E. Smallman (University of Birmingham, England)—Recently, Tedmon and Ferriss11 have determined the yield stress parameters oi and ky for tantalum by measuring the lower yield stress as a function of grain size 2d and fitting the results to a relationship of the form They report that although ky , which is taken to be a measure of the dislocation locking strength, is small (- 2 to 4 x 106 cgs units) a substantial yield drop is nevertheless observed in a normal tensile test. Niobium gives a similar result,12-14 as pointed out in the original work by Adams et a1.,12 and in order to check this apparent anomaly the yield-stress parameters of electron beam-melted niobium have recently been reanalyzed15 by the Luders strain technique. In this method the strain hardening part of the stress-strain curve is extrapolated to zero plastic strain; the intercept on the preyield portion of the curve is taken to give oi, whilst the difference between oi and the lower yield stress gives kyd-1/2. The results indicate that ky increases with increasing grain size and hence, a plot of vs d-112 yields an apparent ky, which is lower than the true value. A similar effect could account for the small ky found in the relatively pure tantalum used by Tedmon and Ferriss. The variation of ky with grain size shows that dislocations are more strongly locked in coarse-grained specimens than in fine-grained samples. In niobium, this may be attributed to the fact that the dislocation density in the fine-grained material is higher than that found in the coarse-grained samples which are given a sufficiently prolonged anneal to remove any residual substructure and, since the metal contains only a small amount of interstitual impurity, a variation in locking occurs. By contrast, application of both the grain size analysis and the Luders strain method to yield-stress data from commercially pure vanadium containing a large amount of interstitial impurity gives consistent values of oi and ky, with ky independent of grain size and temperature. Electron microscope observations show minor variations in dislocation density from grain size to grain size, but in any case in this material the dislocations are heavily locked with precipitate. On yielding new dislocations are generated and, as a consequence, the importance of any differences in dislocation density between the various specimens of different grain size is considerably reduced. It is perhaps significant that Adams and lannucci,16 working with a grade of tantalum containing a higher interstitial content than that used by Tedmon and Ferriss, prepared the specimens of different grain size by annealing in the temperature range 1500" to 2000° C to minimize any differences in dislocation structure, and found that ky had a value of 1.04 x 107 cgs units, independent of testing temperature. Such behavior is consistent with the dislocations being locked by carbide precipitates so that the generation of free dislocations is an athermal process. The recent work of Gilbert et al.17 also shows that in tantalum there is no significant variation of ky with grain size provided it contains 150 ppm of oxygen. In this case, however, the dislocations are not locked by precipitate and ky is temperature dependent. C. S. Tedmon and D. P. Ferriss (authors' reply)— We would like to thank Dr. Smallman for his interesting comments and discussion to our paper, "The Dependence of Yield Stress on Grain Size for Tantalum and a 10 pct W-90 pct Ta Alloy".18 It was suggested that perhaps the relatively small values obtained by us for ky of tantalum could be attributed to the same cause that accounts for the apparently small values of ky that result when it is determined by the Luders Strain technique. Since our values were obtained by plotting the lower yield stress vs the reciprocal of the square root of the grain size, it is not clear how this could be the case. The values of ky in this experiment have been calculated, using the Luders strain technique. With this method, values for ky on the order of 2 x 105 to 5 x lo6 cgs units were obtained. In spite of this rather large variation, the magnitudes are still small, and there appeared to be no good correlation between ky and the grain size or the yield stress, probably because of the difficulty in accurately extrapolating the work-hardening portion of the curve back to zero plastic strain. As was shown in the original data,18 there was little work hardening in any of the curves, at any temperature. In his discussion, Dr. Smallman also points out how ky has been observed to increase with increasing grain size, when determined by the Luders strain technique. There are at least two possible explanations for this. In the first case, if it is assumed that the bulk of the interstitial impurities are concentrated at the grain boundaries, then, of course, the available grain boundary area would decrease with increasing grain size, thus presenting less area for the interstitials, which would then presumably increase the concentration within the grains, thereby increasing the locking of the dislocations. In the second case, the increase in ky with increasing grain size would be attributed to the nature of the grain boundary itself. One of the several ways of deriving the Hall-Petch equation19 is based on the stress concentration arising from a pile-up of dislocations at the boundary. The ability of the stress concentration to unlock a source in a neighboring grain would depend on the strength of the grain boundary. As is well-known, the nature and struc-

Jan 1, 1963

By C.P. Clingerman

The recent iastallation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. The Furnace Proper A few of the characteristic points and dimensions of the furnace proper are: Hearth diameter.............. 26 ft. o in. Bosh diameter............... 29 ft. 1 3/4 in. Stock-line diameter........... 20 ft. o in. Large-bell diameter........... 14 ft. 8 in. Small-bell diameter........... 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed............ 94 ft. 4 in. Height of furnace from center of iron notch to main platform ...................... 105 ft. o in. The furnace top is equipped with a MC-Kee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. 9 in. in diameter, then through uptakes that, are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. Dust Catcher The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catchei is 9 ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is so0 with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas inside the dust catcher. The ratio of the area of the inside cone at its bottom lip to the

Jan 1, 1943

By C. P. Clingerman

The recent iastallation of a combination dust catcher, gas washer and precipitator at Carrie blast furnaces of the Homestead Steel Works has given very satisfactory results. The following description of the gas-cleaning installation is based on actual operating experience. When Carrie blast furnace No. 3 was rebuilt the decision was made to fine-clean all the gas produced by the furnace, because the management wanted fine-cleaned gas for fuel in the stoves and boilers. In order to keep the installation cost as low as possible, the gas-cleaning system was streamlined. All by-pass lines and goggle valves for bypass lines were eliminated from the system. A radical departure from the use of 8-in. tubes in the Cottrell-type precipitators was made by using 12-in. diameter tubes in a single compartment, the single compartment being divided into two units by a single partition wall in the top header. The Furnace Proper A few of the characteristic points and dimensions of the furnace proper are: Hearth diameter.............. 26 ft. o in. Bosh diameter............... 29 ft. 1 3/4 in. Stock-line diameter........... 20 ft. o in. Large-bell diameter........... 14 ft. 8 in. Small-bell diameter........... 6 ft. 6 in. Height of furnace from center of iron notch to bottom of large bell, closed............ 94 ft. 4 in. Height of furnace from center of iron notch to main platform ...................... 105 ft. o in. The furnace top is equipped with a MC-Kee revolving distributor, the operation of which is electrically interlocked with the skips, bell hoists, and coke-weighing and charging apparatus through a Freyn automatic charging control. The gas leaves the furnace first through four offtakes, 5 ft. 9 in. in diameter, then through uptakes that, are approximately 85 ft. high, which feed into a single down-comer that is 9 ft. in diameter. Dust Catcher The primary dust catcher installed (Fig. I) may be described as a single-cone type. The inlet pipe at the top of the dust catchei is 9 ft. in diameter; it is flared to a conical shape as it extends down inside the dust-catcher shell, which is 35 ft. in diameter, 37 ft. high on the straight side, and has a conical top and bottom. The slope of the bottom is so0 with the horizontal. The cone-shaped pipe inside the dust-catcher shell is 42 ft. high and is 19 ft. 7 in. in diameter at its bottom lip where it releases the gas inside the dust catcher. The ratio of the area of the inside cone at its bottom lip to the

Jan 1, 1943

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970

By W. I. Garms, J. L. Stevens

Because of the many conflicting opinions regarding the functioning of the ball load and the characteristics of ball wear in ball-mill grinding, the following résumé of reports covering recent tests conducted at the Hayden plant of the Kennecott Copper Corporation is submitted with the view of pointing out certain salient features that should throw additional light on the subject. Mills Used Cylindrical drum mills with trunnion feed and discharge were used. The discharge trunnion was 13½ in. in diameter. Dimensions inside the lining were 6 ft. 6 in. in diameter and 9 ft. 6 in. long. The mills were Britannia-lined and nine lifter bars projected 2 in. from the lining. The mill speed was 162/3 r.p.m. Feed to the mill was 9 per cent on 10-mesh, 85 per cent on 100-mesh, 77 per cent solids. New balls measured 2 in. in diameter and the approximate weight of the ball load was 40,000 pounds. Initial Test During a test that was being conducted to determine the relative economic value of standard cast balls vs. forged steel balls in the local 'grinding operation, certain observations were made in regard to the functioning of the various ball sizes and the characteristics of ball wear, which warranted a supplementary test for the purpose of confirming such observations. For the initial test, the necessity for developing a graduated load of the new forged balls before the test could be started was realized, but the time required to obtain a graduated load and the functioning of the various ball sizes was not clear. No advantage could be seen for starting out with a full load of forged balls, as this initial load, at the least, would have to be completely ground out and replaced by daily additions of balls before the graduation could be complete and a normal static condition of ball sizes reached. For a considerable period prior to exhaustion of this initial charge there would be an unusual quantity of worn balls of a certain size, which would not be typical of a normal charge and could influence the characteristics and functioning of the entire load. Therefore, it was decided to start by daily addition of the forged balls to a mill that contained a normal operating load of cast balls. After 88 days of operation the mill was shut down for inspection. By that time the load consisted of a mass of forged balls functioning around a large core of the residual material of the former cast-ball load. This core of cast slugs, locally referred to as "the kidney," was well defined from the forged-ball load.

Jan 1, 1947

By W. I. Garms, J. L. Stevens

Because of the many conflicting opinions regarding the functioning of the ball load and the characteristics of ball wear in ball-mill grinding, the following résumé of reports covering recent tests conducted at the Hayden plant of the Kennecott Copper Corporation is submitted with the view of pointing out certain salient features that should throw additional light on the subject. Mills Used Cylindrical drum mills with trunnion feed and discharge were used. The discharge trunnion was 13½ in. in diameter. Dimensions inside the lining were 6 ft. 6 in. in diameter and 9 ft. 6 in. long. The mills were Britannia-lined and nine lifter bars projected 2 in. from the lining. The mill speed was 162/3 r.p.m. Feed to the mill was 9 per cent on 10-mesh, 85 per cent on 100-mesh, 77 per cent solids. New balls measured 2 in. in diameter and the approximate weight of the ball load was 40,000 pounds. Initial Test During a test that was being conducted to determine the relative economic value of standard cast balls vs. forged steel balls in the local 'grinding operation, certain observations were made in regard to the functioning of the various ball sizes and the characteristics of ball wear, which warranted a supplementary test for the purpose of confirming such observations. For the initial test, the necessity for developing a graduated load of the new forged balls before the test could be started was realized, but the time required to obtain a graduated load and the functioning of the various ball sizes was not clear. No advantage could be seen for starting out with a full load of forged balls, as this initial load, at the least, would have to be completely ground out and replaced by daily additions of balls before the graduation could be complete and a normal static condition of ball sizes reached. For a considerable period prior to exhaustion of this initial charge there would be an unusual quantity of worn balls of a certain size, which would not be typical of a normal charge and could influence the characteristics and functioning of the entire load. Therefore, it was decided to start by daily addition of the forged balls to a mill that contained a normal operating load of cast balls. After 88 days of operation the mill was shut down for inspection. By that time the load consisted of a mass of forged balls functioning around a large core of the residual material of the former cast-ball load. This core of cast slugs, locally referred to as "the kidney," was well defined from the forged-ball load.

Jan 1, 1947

By J. R. Lewis

During the past few years there has been considerable interest in the sizing and the preparation of the iron ore fed into blast furnaces. Furnacemen know that proper sizing of ore tends to increase the efficiency of the furnace. It has been shown by Joseph1 and his associates that there is a direct relationship between the porosity of an ore particle and the time required for its reduction in the blast furnace. This relationship may be stated as follows: All other factors remainig constant, the time for reduction of a given sample of ore is inversely propor-tiofid to its porosity. As a consequence, large pieces of very porous ore, say 3 or 4 in. in cross section, will be completely reduced by the time they reach the hot zone just above the tuyeres, while large pieces of dense, nonporous ore may reach the hot zone with their centers unreduced. This means that for the latter complete reduction will be accomplished by the so-called "direct method;" i,e., where carbon reacts directly with the ore. Some recent work by philbrook2 seems to contradict this rule. He found that of two unlike ores he studied, the one with the lower porosity reduced more readily. He explained his results as "possibly due to an apparently greater tendency of the rA, ore (lower porosity) to crack during preliminary dehydration and during reduction." This brings his results in line with the rule stated above. It is not the author's intention to enter into a discussion of the merits of "direct" versus "indirect" reduction. It is enough to Say that, in general, indirect reduction is desirable. For the greatest efficiency, Gruner's theorem3 requires that all reduction in the blast furnace be indirect. Joseph seems to believe this also, because in his recent article on Some Comparisons between Iron Ore, Sinter and Nodules as Blast Furnace Feed4 he concludes that: "In genera', the carbon in blastfurnace coke is used most efficiently when the largest amount of the carbon charged reaches the tuyeres." However, P. V. hlartin,3 in an excellent paper, has shown that some direct reduction may actually increase the efficiency of the furnace; that is, increase its rate of production while maintaining maximum fuel economy. For nonporous ores there is more opportunity to have an excess of direct reduction unless the factors that make for indirect reduction are favored; for instance; the Proper sizing of the Ore particles' Another factor that has an important bearing on the reduction rate, as it is affected by particle size, is the flow of heat into the particle. The ore particle

Jan 1, 1948

By J. R. Lewis

During the past few years there has been considerable interest in the sizing and the preparation of the iron ore fed into blast furnaces. Furnacemen know that proper sizing of ore tends to increase the efficiency of the furnace. It has been shown by Joseph1 and his associates that there is a direct relationship between the porosity of an ore particle and the time required for its reduction in the blast furnace. This relationship may be stated as follows: All other factors remainig constant, the time for reduction of a given sample of ore is inversely propor-tiofid to its porosity. As a consequence, large pieces of very porous ore, say 3 or 4 in. in cross section, will be completely reduced by the time they reach the hot zone just above the tuyeres, while large pieces of dense, nonporous ore may reach the hot zone with their centers unreduced. This means that for the latter complete reduction will be accomplished by the so-called "direct method;" i,e., where carbon reacts directly with the ore. Some recent work by philbrook2 seems to contradict this rule. He found that of two unlike ores he studied, the one with the lower porosity reduced more readily. He explained his results as "possibly due to an apparently greater tendency of the rA, ore (lower porosity) to crack during preliminary dehydration and during reduction." This brings his results in line with the rule stated above. It is not the author's intention to enter into a discussion of the merits of "direct" versus "indirect" reduction. It is enough to Say that, in general, indirect reduction is desirable. For the greatest efficiency, Gruner's theorem3 requires that all reduction in the blast furnace be indirect. Joseph seems to believe this also, because in his recent article on Some Comparisons between Iron Ore, Sinter and Nodules as Blast Furnace Feed4 he concludes that: "In genera', the carbon in blastfurnace coke is used most efficiently when the largest amount of the carbon charged reaches the tuyeres." However, P. V. hlartin,3 in an excellent paper, has shown that some direct reduction may actually increase the efficiency of the furnace; that is, increase its rate of production while maintaining maximum fuel economy. For nonporous ores there is more opportunity to have an excess of direct reduction unless the factors that make for indirect reduction are favored; for instance; the Proper sizing of the Ore particles' Another factor that has an important bearing on the reduction rate, as it is affected by particle size, is the flow of heat into the particle. The ore particle

Jan 1, 1948

By G.A. Moore, C. E. Sims

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949

By C. E. Sims, G. A. Moore

In previous publications of the writers4-7 it has been shown that vacuum extraction of steel can be carried as close to quantitative completion as desired provided the steel is in the austenitic state and sufficiellt time is allowed. For precise work, the method claims preference because the equipmelit for holding and heating the sample can be made simple, and because crucibles, boats, and other unnecessary materials can be eliminated and the blanks thus made very small. It is well known that the evolution rate of hydrogen is smaller just above the trans. formation than immediately below, as would be expected from the increase in solubility when passing into the gamma state. Many attempts have been made to obtain analyses by extraction just below the transition, using times of approxi. mately 2 hr. while it is true that the rate of evolution drops nearly to zero under these conditions, it has repeatedly been shown that the process is incomplete since on raising the temperature into the austenitic range, evolution will be resumed, usually after a, considerable induction period. The low-temperature evolution process appears to be useful in some cases for comparative tests where the residual crror may be more or less constant between samples, For general use, however, there is no guarantee that the error caused by incomplete extraction is constant; hence, the more laborious but more reliable high-temPe'atu'e Process must be used. At high temperature, an original flash evolution, similar to that at lower temperature, is first observed. After not more than an hour, the flash subsides and cvolution settles down to a regular first-order reaction rate for which the half-life* is usually of the order of a few hours for the 5/8-in. diam cylinder at 1050°C. The regular evolution may be followed for whatever period appears justified, after which the residual gas may be estimated as equal to that which was evolved in the last observed half-life period. Tests have shown that the composition of the evolved gas does not vary greatly during the progress of evolution; therefore the residual gas may safely be taken to have the same composition as the portion col-

Jan 1, 1949

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a' phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a' phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.' Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a', with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a' phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a'. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By James T. Gow, Oscar E. Harder, Anton de S. Brasunas

This paper deals with the results obtained and the techniques employed in determining: 1. Liquidus and solidus temperatures of the HH and HT type heat-resistant alloys. 2. The relation of true temperatures (thermocouple) to apparent temperatures (optical pyrometer) for the molten HH and HT type alloys. This work was the outgrowth of needing to know something definite about these temperatures in order to study the effect of pouring temperatures, shake-out times, and heat-treatments on the properties of some heat-resistant alloys. The information developed is thought to be of interest to industry for guidance in foundry practices and the industrial heat applications of the alloys. This paper is based upon work that has been done for the Alloy Casting Institute at Battellc Memorial Institute. Liquidus and Solidus Temperatures of HH and HT Type Alloys Experimenta1 Procedures Temperature-time curves were obtained during the cooling and solidification of several HH and HT type alloys. The metal was melted in an Ajax high-frequency, induction furnace and poured into a core-sand mold for cooling. The temperature measurements were obtained by means of a platinum, platinum-rhodium thermocouple contained within a fused silica sheath, which was extended through the side wall of the dry core-sand mold to a point at about the center of the mold cavity, which was 3 in. in diameter by 5 in. deep. The cold junction of the thermocouple was kept in an ice bottle, and the temperature was recorded automatically on a direct-reading potentiometer recorder. Through a switching arrangement, the temperature recorded was checked occasionally with a portable Leeds and North-rup potentiometer indicator. Less than a 5°F. variation in the two instruments was always found. This is within the limit of accuracy of readings. The thermocouple used was checked for accuracy against a standard couple, both before use on this work and after completion of the work, by the instrument laboratory. Temperature-time Cooling Curves Fig. I is an enlarged reproduction of a part of one of the cooling curves over the temperature range of 2600' to 2200°F. for an alloy of the HT type with 0.45 per cent carbon, 16 per cent chromium, and 36 per cent nickel. This is a typically shaped cooling curve as obtained for the alloys. It will be noted that two temperatures "re shown on Fig. I for the liquidus temperature. It is thought likely that the higher temperature, A, at the point at

Jan 1, 1945

By H. Conrad, V. V. Damiano, G. J. London

A method is described for producing single crystals of high-purity beryllium, Be-4.37pct Cu, and Be-5.24 pct Ni. These crystals were prepared for testing in compression parallel to the [0001] by orienting and lapping to within ±3' of arc of the (0001). Microstrain testing apparatus is described along with c axis compression results for ingot purity beryllium, twelve-zone-pass material, and the above-mentioned alloys. Results show no measurable plasticity for the ingot purity material from -196" to 400°C, although some surface traces of (1122) slip was observed at 200°C and above. The twelve-zone-pass material shows substantial microstrain plasticity at 220°C with slip on (1122). Both alloys show significant plasticity at room temperature and above with slip also on (1122) planes. THE two slip systems which normally operate during the plastic deformation of beryllium in the vicinity of room temperature are:' basal slip (0001)(1120) and prism slip . Pyramidal slip with a vector inclined to the basal plane has been reported for elevated temperatures,'-a but occurs near room temperature only at very high stresses.~ A summary of the available data on the effect of temperature on the critical resolved shear stress for slip on these systems has been compiled by Conrad and Perlmutter.~ It has been postulated6'7 that one of the principal factors contributing to the brittleness of poly crystalline beryllium at temperatures below about 200°C is the difficulty of operating pyramidal slip with a vector inclined to the basal plane. Hence, detailed information on the operation of such a slip system is important to understanding the brittleness of beryllium. The operation of pyramidal slip with a vector inclined to the basal plane is best accomplished in beryllium by compressing single crystals in a direction parallel to the c axis. In such a test the resolved macroscopic shear strzss on the basal and prism planes is zero and (1012) twinning which is favored by tension along the c axis does not occur. Hence, in c axis compression of beryllium the normal deformation modes are inhibited and the operation of pyramidal slip with a vector inclined to the basal plane is favored. In the present investigation, c axis compression tests were performed on beryllium single crystal as a function of temperature (77" to 700°K), purity (commercial and twelve zone pass), and alloy content (4.37 wt pct Cu and 5.24 wt pct Ni). Presented here is a description of the test techniques employed and the gross mechanical behavior observed. A detailed analysis of the slip traces developed on the surfaces of the deformed specimens during these tests and the results of electron transmission studies of the deformed crystals are given in a separate paper.B PROCEDURE 1) Materials and Preparation. Single crystals about 1 in. diam were prepared of the following materials: commercial-purity beryllium, high-purity beryllium, and two beryllium alloys, one with 4.37 wt pct Cu and the other with 5.24 wt pct Ni. The commercial-purity single crystals were obtained by cutting specimens from large-grained ingot of Pechiney SR material, which is approximately 99.98 pct pure. The high-purity crystals were prepared by floating-zone refining (twelve passes) a rod (7 in. by 1 in, diam) of Pechiney SR grade cast and extruded beryllium. Although an absolute chemical analysis of the zone-refined material was not established, mass spectro-graphic analysis, emission spectrographic analysis, and y activation analysis indicated that it contained in atomic fractions about 5 to 10 ppm each of carbon and oxygen, 1 to 5 ppm each of nickel and iron, and about 1 to 2 ppm of copper, with the remaining residual impurities being less than 1 ppm. Further indication of the purity of this material is provided by the critical resolved shear stress for basal slip, which was approximately 300 psi. The starting material for the alloy single crystals was 1-in.-diam floating-zone-refined (six passes) rod of Pechiney SR grade beryllium. Two such rods were wrapped respectively with sufficient weight of wire of high-purity copper (99.999 pct) or nickel (99.999 pct) to yield a 5 wt pct alloy. A seventh floating-zone pass was then applied to each of the rods to accomplish the initial alloying and an eighth pass for homogenization. Analytical samples were taken from regions of the rod immediately adjacent to where the mechanical test specimens were cut; these indicated 4.37 wt pct Cu and 5.24 wt pct Ni. 2) Crystal Orientation. To avoid the occurrence of basal slip during c axis compression testing, it is necessary to load the crystals as nearly parallel to the c axis as possible. Preliminary c axis compression tests indicated that plastic flow and/or fracture occurred at stresses of the order of 300,000 psi; hence on the basis of a critical resolved shear stress for basal slip of 300 to 400 psi, the maximum crystal misorientation permitted is about 4 to 5' of arc. Since this accuracy cannot be obtained using the usual back-

Jan 1, 1969

Philip Argall, Denver, Colo. (communication to the Secretary) : Mr. Rickard expresses regret that I have not given more extracts " from the fresh leaves of nature's open book." The quotations used by me in argument were all from nature's open book, and by authorities recognized in the scientific world as being able to decipher nature's unwritten pages, if not lay bare her inmost secrets. The study of -nature should be preceded by a knowledge of her laws. Natural science is but the summary of the observations of the past or an organized and accurate knowledge of the order in which things have been observed to happen. One who ignores the 'knowledge of the past or despises that of the present and approaches nature's open book with a virgin mind but too often finds her

Jan 1, 1895

The present paper records a chapter in the history of the development of an electrolytic manganese industry in the United States.l A relatively large pilot plant at Boulder City, Nev., for the production of electrolytic manganese was conceived as part of the national defense program to make this country independent of foreign importation of manganese ore. The first authorization, in November 1940, however, was for a plant of only several hundred pounds capacity. Improvements in process and subsequent additions to some sections authorized by subsequent appropriations have enabled the plant to produce as much as 2000 lb. of manganese a day for substantial periods of time. Since in pilot-plant operation frequent changes are made in the flowsheet, the electrolytic manganese plant was constructed so that equipment could be rearranged with a minimum of expense and time. Several different kinds of the various ¦ types of equipment were installed for many of the operations, so that the one most suitable for the process might be chosen. Pilot-plant operations were begun in November 1941 and have been continuous except for brief shutdowns for installation of new equipment. More than one-half million pounds of manganese have been produced. The improvements in process, selection of equipment, and operational procedure developed are recorded here. Development of the Process The work of early investigators on the electrolysis of manganese solutions has been reviewed by Shelton. Until the method of continuous production of manganese by electrolysis was perfected by SheltonZm4 and coworkers, no practical procedure had been devised. The method as originally developed by the Bureau of Mines will be described here only briefly. The manganese dioxide ore was reduced in a rotating kiln-type furnace at 650°C. in an atmosphere of "city" gas. The calcine was leached with spent electrolyte and enough sulphuric acid to produce a neutral leach solutioil containing 2 5 grams manganese per liter as manganese sulphate and zoo grams per liter of ammonium sulphate. Arsenic was removed from the solution by the addition of 0.0j gram iron per liter as ferrous sulphate followed by oxidation with manganese dioxide, and aeration, which precipitated the iron as ferric hydroxide. The solution, free from iron

Jan 1, 1944

By Jerome F. Kuzmick

The use of iron powder during the postwar conversion period has been increasing with great rapidity. This is particularly true in regard to the manufacture of molded mechanical parts such as bushings, gears, cams, small wheels, and the like. Many manufacturers have found it possible to replace machined cast iron and carbon steel with molded iron powder parts, and thereby can not only effect a savings in cost, but can produce a better product as well. As the field of application for iron powder parts widens, greater demands are made upon the powder supplier concerning quality and uniformity characteristics. The following are some of the most important properties parts fabricators desire in the iron powder they use: 1. The powder should have high compressibility so that good density can be obtained without the use of excessive pressures. At the same time, it should show low die wear so that a large number of pieces can be produced from the die. This means that the powder must be of high purity and good softness or plasticity. 2. The powder should produce compacts of high green strength, so that unsintered parts can be handled without breakage or fraying of the edges. 3. The sintering properties should be good so that satisfactory strength is obtained in the sintered piece. 4. Compacts made from the powder should show small but, above all, uniform dimensional changes during the sintering operation so that accurate parts can be produced, and warping and other such bad effects eliminated. 5. The powder should have satisfactory flow properties for automatic molding. 6. It is very important that the powder be uniform in sieve analysis, compressibility, flow, purity, and other qualities, from container to container in any given lot and from shipment to shipment. 7. Price—The fabricators desire all these good properties, but in many instances still do not wish to pay a premium price. There has been considerable discussion as to the importance of price of the powder in relation to the cost of the finished product. It is true that in cases where certain special properties only procured by powder metallurgy are required, price is not a criterion. On the other hand, there have been a number of applications recently made which would not be commercially practical with a powder which commands a premium in price. Iron powder parts are compressed in automatic presses to definite size, shape, and density. The powder is compressed to a density figure dependent upon the function the part is to perform, as well as upon such important considerations as press capacity and die wear. Such parts can be roughly broken down into the following density ranges:

Jan 1, 1949

By J. F. Keefe, C. J. Bier, O&apos

This study was carried out with copper because it represents the simplest form of sintering, in that but one metal is involved and all reactions occur in the solid state. The present work will cover three variables affecting the sintering process; namely, briquetting pressure, sintering temperature and time in hot zone. Although strength and dimensional changes were observed, this is primarily a metal-lographic study of the sintering process in copper. The term "sintering" should be understood to mean the process by which the metal powder particles of the compact become united into one body. Material Used The copper powder used was made from reduced copper oxide, and is typical of a grade used for the mass production of parts formed of metal powders. The screen analysis of the powder was as follows: Per Cent Per Cent BY BY Particle Size "Weight Particle Size "Weight Mesh Microns /80.... 0.00 43/32.... 17.49 80/I00..... 32/20......16.68 100/140.... 0.34 20/10.... 23.14 140/200___ 15.25 10/5..... 4.64 200/230....... 5.00 5/0...... 0.75 230/325.... 16.70 — 325....62. 69 The minus 325-mesh analysis was made by using a Roller Air Analyzer.1,2 The apparent density is here defined as the weight per cubic centimeter of the loose, unpacked powder as measured with the Hall flowmeter. The value for the powder used was 2.57 grams per cubic centimeter.

Jan 1, 1945

By S. Lipson, H. W. Antes, H. Rosenthal

A study was made of the effect of ingot structure on the strength and ductility of high-strength wrought-aluminum alloys. It was found that a fine-cast structure facilitated complete homogenization which, in turn, resulted in significant increases in ductility and strength. A completely homogenized 7075-T6 alloy developed tensile properties of 85,000 psi UTS, 75,000 psi YS, with 40 pct RA. Completely homogenized 7001-T6 alloy tensile properties were 102,000 psi UTS, 99,000 psi YS, with 19 pct Ra. A method was devised for making small ingots having secondary dendrite arm spacing of less than 10 u. This method involved multiple-pass arc melting of commercial rolled plate with a tungsten electvode. This material could be completely homogenized after 3 hr at 900°F; homogenization of the original plate material was not complete after 120 hv at 900°F. Degree of homogeneity was determined by use of metallographic and electron-microprobe analyses. The electron-micro-probe study also showed the preferential segregation of solutes in the microstructure. HIGH-strength aluminum alloys, such as those of the 7000 series, usually freeze by the formation and growth of dendrites. The dendrite arm spacing (DAS) depends on the rate of solidification.' Commercial ingots are usually direct chill-cast to promote more rapid solidification, but, due to the large mass of the ingot, localized solidification times are long and a large DAS results. During solidification, solute elements are rejected by the solid as it forms, causing enrichment of the liquid and ultimately solute-rich interdendritic regions. In order to attain a homogeneous ingot, the segregated solutes must diffuse across the dendrite arms. The larger the DM, the longer the time for complete homogenization. In the case of commercial ingots, the DAS is so large that the time for complete homogenization is prohibitively long and, therefore, second phases or compounds are always present. These un-dissolved phases are carried over to the wrought material during processing, resulting in an impairment of strength and ductility. In addition, the mechanical fibering of the undissolved second phases or compounds during working results in mechanical property anisotropy. If complete homogenization could be attained, higher ductility could be expected. The realization of higher ductility at current strength levels is a desirable objective; however, if higher-strength alloys were wanted, it might be possible to sacrifice some of this ductility by adding more solute elements and produce even higher-strength alloys than are currently available. Further, if complete homogenization leads to more efficient utilization of solute elements, then more dilute alloys should have relatively high strengths with very high ductility. In all instances, it would be expected that the degree of mechanical property anisotropy due to mechanical fibering would be reduced. Therefore, it was the purpose of this investigation to produce cast structures that would facilitate homogenization and to determine the effect of homogenization on the properties of high-strength, wrought-aluminum alloys. MATERIAL CLASSIFICATION Commercial Alloys. In order to illustrate the non-homogeneous condition that exists in commercial high-strength, wrought-aluminum alloys, typical micro-structures of 7001, 7075, and 7178 are shown in Fig. 1. The chemical compositional specifications of these alloys are given in Table I. It can be seen in Fig. 1 that a considerable amount of undissolved second-phase material is present in each of these alloys. The solute elements associated with the undissolved phases were identified by electron microanalyses. Back-scattered electron images and characteristic X-ray images of the three commercial alloys are shown in Figs. 2, 3, and 4. These data indicate that the second phases are regions of high copper and high iron-copper concentrations. The second-phase material also was analyzed for magnesium, zinc, manganese, chromium, and silicon, but no significant enrichment above that of the matrix was found. Therefore, the problem of homogenization resolved itself into one of dissolving the copper-rich and the iron-copper-rich second phases. In order to accomplish this objective, two approaches were made. The first was to reduce the iron as low as possible since this element has a maximum solid solubility of 0.03 pct in aluminum. The second was to produce cast structures with finer DAS to facilitate dissolving the second phases. Commercially Produced High-Purity Alloys. A special high-purity, 2000-lb ingot of 7075 alloy was made by a commercial producer. This alloy contained the following weight percentages of solutes: 5.63 Zn, 2.48 Mg, 1.49 Cu, and 0.21 Cr. All other elements combined were less than 0.02 pct by wt including iron and silicon at less than 0.01 pct each. The ingot was cast and processed into rolled plate using standard commercial techniques. Microstructures of standard commercial 7075 and the special high-purity 7075 are shown in Fig. 5. It can be seen from this figure that the high-purity alloy has less undissolved second-phase material, but a significant amount was still present. The second phase in the high-purity material did not contain iron but it was found to be enriched with copper. The slight effects of the increased purity and de-

Jan 1, 1968

By L. M. Cathles, L. E. Murr

Results of two years of leaching of 160 metric tons of low grade industrial copper sulfide waste in a large (40` high 10` diameter) thermally insulated tank at the New Mexico Institute of Mining and Technology are analyzed in the light of a previously developed model of the waste leaching process. It is shown that the model is verified in all major aspects and that the parameters in the model that characterize the leaching of a particular sulfide waste are usefully constrained by the results of the tank leaching experiment. The similarity between waste leaching parameters determined from the tank experiment and from interpretation of the leach behavior of test dumps constructed of similar waste encourages optimism it may be possible to predict the leach behavior of field dumps from suitably interpreted column experiments using the computer model developed.

Jan 1, 1980