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By H. H. Richardson, E. H. Dix

Of all the alloying elements used in commercial aluminum alloys, copper stands out as by far the most important, and it is perhaps for this reason that the constitution of the aluminum-copper system has received the attention of a number of experimenters covering a period of approximately 20 years. It would be expected that during this time the equilibrium relations would have been thoroughly and exactly worked out. In a general way this is true, but there is a surprising lack of agreement in the details of the high aluminum end of the diagram, particularly in regard to the solid solubility of copper in aluminum, which has been given variously as 2 per cent. to 5 per cent. at the eutectic temperature. The importance of this is much greater than might at first appear to one unfamiliar with modern commercial aluminum alloys. This is true because, with one exception, the susceptibility of the strong alloys to heat treatment depends, in part at least, upon the solid solubility relations of copper in aluminum. In 1919, Merica, Waltenberg, and Freeman1 published the first detailed information on these solubility relations. They found that the solubility of copper decreases with falling temperature from about 4 per cent. at 525" C. to about 1 per cent. at 300" C. and is apparently still diminishing at lower temperatures. In 1921 there was published a brief account of the results obtained in the National Physical Laboratory, Teddington, England.2 This laboratory, however, reported that 5 per cent. of copper is soluble in aluminum at 540" C., and that this amount decreases to about 3 per cent. at 20" C. In the same year Ohtani and Hemmi3 reported a solubility of 4.8 per cent. copper at 520" C., 2.6 per cent. at 460" C. and 1.5 per cent. at 420" C.

Jan 1, 1926

By C. C. Harris

An analytical solution of the integro-differential equation of batch grinding is proposed as a first appoximation to the xYt surface. The size distribution equation (xY plane) is a three parameter equation previously suggested. Possible refinements are outlined. Comminution kinetics research is presently following several related courses. Some are equivalent, in that they represent different ways of viewing the same facet of the problem, though the entire endeavor cannot be described as being completely integrated. The purpose of this note is to propose and discuss a framework into which the various approaches might be fitted. This must clearly be founded upon an analysis of the xYt surface.' (See also Fig. 1 of Reference 26.) The investigations referred to above comprise mainly researches into the following: (1) The kinetics of the creation of the finer sizes during relatively small grinding times. This is the Fahrenwald-Arbiter-Bhrany 2-3 approach which leads to equations equivalent to a special case of the charles4 relationship. It emerges that initial production of fines follow essentially zero order* kinetics. (2) Disappearance kinetics of the coarser fractions. This appears to be a first order relationship.5-6 (3) Prediction of the xYt surface via the selection and breakage functions utilizing computer-programmed or approximate solutions of the integro-differential equation of batch grinding.5,8-17 A recent discussion by Mika et al.5 references the relevant literature up to about 1966. In addition to these main-stream researches there is some work on the minor topic of extremely long grinding time considered as a limiting case.18-19 The field is supported by investigations into the size distribution of fragments produced by breakage processes, some of this work being most valuably statistical-mechanical in nature.20-25 Better fitting equations, however, are obtained by statistical and curve-fitting methods.26 This

Jan 1, 1969

By Lo-Ching Chang, K. M. Goldman

The kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was, simple. A graphite crucible 15/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an in- duction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature for 3-5 "'in., aftcr which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 mi11. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the ternperature of the furnace in 1 to 1 1/2 min. Slag

Jan 1, 1949

By K. M. Goldman, Lo-Ching Chang

The kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was, simple. A graphite crucible 15/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an in- duction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature for 3-5 "'in., aftcr which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 mi11. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the ternperature of the furnace in 1 to 1 1/2 min. Slag

Jan 1, 1949

E O'C Acker '86 Jinzoc Adachl '88 Frederic R Abbe '97 T H Aldrich '96 Truman H Aldrich '78 Walter H Aldridge '89 Anson W Allen '87 John H Allen '84 Thomas Andrews '94 William R Appleby '90 R M Atwater, Jr '97 Lawrence Austin '82 S Ayres '73 H Foster Bain '97 David Baker '86 John Henry Banks '83 Henry C Banon '90 Thomas J Barbour '97 Alonzo F Bardwell '89

Jan 1, 1952

By D. R. Parrish, V. J. Berry

Reverse combustion is one thermal method of recovering hydrocarbons from porous undergrortnd formations containing oil or tar. In applying this method, air is introduced via an injection well and the mixture of air and hydrocarbons is ignited in the production well. A combustion zone then recedes toward the injection well, counter-current to the air flow. If the combustion-zorie temperature is sufficiently high, the oil or tar irz place is distilled arid cracked. The hydrocnrhon flows as a vapor to the production well and subsequently is condensed at the surface. Maximum temperature and velocity of morcment arc the two dependent variubles defining the progress of the combustion zone. A theoretical analysis has been made of heat flow in the reverse-comhustion process as.srtrning linear flow in a homogeneous system. The differentirll equatious, which include the oxygen-hydrocar-hon rctrction rate, have been solved numerically. Rescllts indicate that the maximum temperature reached and he cornbustion-zone relocity both increase with an incrense in air-injection rote. Heat loss to surroundings has little effect on the maximum comhustion-zone ten?perature achieved, but it is reflected in a reduced com-bustion-zorzc, velocity. It is also predicted that an increase in the oxygen-hydrocarbon reaction rate results in a reduction in the maximum temperature reached. The calculated results are in agreement with results from reverse-combustion experinments using samples of a tar sand. INTRODUCTION Reverse combustion is one thermal method of recovering hydrocarbons from porous underground forma-tions containing oil or tar.' In applying this method, air is introduced into the underground formation via an in-jection well. In one or more adjacent production wells, the mixture of air and hydrocarbons is ignited at the sand face. The combustion zone thus formed recedes toward the injection well, counter-current to the air flow (Fig. 1). Under certain conditions, the rate of recession of the combustion zone is sufficiently rapid that only a small fraction of the hydrocarbon at any point in the formation is consumed by combustion. If the combustion-zone temperature is sufficiently high, the uncon-sumed oil or tar in place may be partially distilled or cracked. This material then can flow as a vapor with the gaseous combustion products to the production well and subsequently be condensed at the surface. Under other conditions, the combustion-zone temperature may be so low that little, if any, of the hydrocarbon is vaporized. Nevertheless, the viscosity of the hydrocarbon may be reduced enough so that other recovery methods subsequently can be applied to produce oil at attractive rates. The maximum temperature achieved in the combustion zone and the velocity of movement are the two dependent variables defining the progress of the combustion zone. Presumably. knowledge of these factors will permit estimates to be made of oil recovery efficiency, oil and gas producticn rates and average amount of injection air required per barrel of oil recovered. The maximum temperature and combustion-zone vclocity are, in turn, expected to be dependent upon air flow rate, heat losses to surrounding formations, physical properties of the rock and the hydrocarbon. the extent to which the porous formation is saturated with the hydrocarbon, the rate of oxidation of the hydrocarbon and the amount of heat released. It is desirable that the relative importance of each of these factors be understood so that the results of laboratory tests of oil recovery by reverse combustion can be properly interpreted in terms of expected field performance. It is particularly desirable to assess the importance of heat lcsses because these are difficult to control or eliminate

By John B. Hastings

THE occurrence of such a large amount of gold in the Hartsel granite, even though the surmised existence of similar areas is not new, brings freshly to mind the pegmatite type of magmatic differentiation lately brought again to attention by occurrences at Silver Peak, Nev., described by Spurr; and in Alaska, described by both Spurr and Brooks. In both localities graunitic rocks or dikes are thought to pass into metalliferous quartz-veins. An interesting association in this connection is the occurrence of diamonds in residual pegmatitic clay of San Juao de Chapado, Brazil, described by Derby :1 (P. 142) "Bodies of pegmatite are quite common in the older rocks of Brazil, both in the. diamond regions and elsewhere, occurring not only in the gneiss and granite, but in the schistose series as well. Those that have been examined are dike-like in their mode of occurrence and granitic in composition." (P. 143) "The question of the eruptive or secretionary origin of pegmatites has long been a subject of discussion among geologists. . . . The recent studies . . . seem to have clearly established that most if not all of them are essentially eruptive masses, though possibly modified in some way by aqueous agencies. Even before becoming acquainted with the literature of the subject this view had seemed to me to be the only acceptable one as regards the typical pegmatites of Brazil." What is pegmatite ? J. F. Kemp says ". . . veins or dikes-it is an open question which is the more correct term-are met formed of very coarsely crystalline aggregates of the same minerals that constitute granite. These are called pegmatite and in them is the home of graphic granite, the curious intergrowth of quartz and feldspar, such that a cross fracture of the blades of quartz suggests cuneiform characters. . . . In regard to the larger veins or dikes it seems improbable that true igneous fusion could have afforded such coarsely crystalline aggregates, and so we are forced to assume such abundance of steam and other vapors, i.e, mineralizers, as to almost, if not quite, imply solution."

Jan 5, 1908

By R. Bakish, W. D. Robertson

IN the course of a study of stress corrosion cracking of AuCu,, it was necessary to develop new electropolishing and metallographic etching methods. The techniques are generally useful for Cu-Au alloys, including the AuCu composition in which transformation markings are well delineated. For electropolishing, the only satisfactory electrolyte and procedure that has been found1 has the composition given in Table I. The solution must be vigorously stirred while polishing and the temperature maintained in the range of 55" to 62°C. The electrolyte is very unstable and can be used only for 10 to 15 min after which its color changes and a dark-brown precipitate forms. The polishing time is between 1 and 4 min depending on the initial surface preparation. The use of a hood is recommended to avoid the danger of cyanide gas which may form at one of the electrodes even though the solution is alkaline. The optimum current and voltage conditions for vertical anode and platinum cathode are on the plateau shown in Fig. 1, in which voltage is measured across the cell terminals. At voltages below the plateau, etching of grain boundaries occurs and under some conditions, which have not been clearly defined, octahedral etch figures are observed. For general purpose grain-size determination in polycrystalline alloys, a 3 pct solution of iodine in methyl alcohol is used with excellent results. However, when it is necessary to reveal small orientation differences or concentration gradients in an alloy, the iodine etch is not satisfactory. For this purpose, a highly satisfactory etching procedure was developed during this investigation. It involves the use of the vapor given off by freshly prepared aqua regia. The solution employed is 3HC1 to lHNO, which decomposes in accordance with the reaction HNO, + 3HC1 = NOCl + 2H,O + Cl,. The polished specimen surface is held about 1 to 2 cm above an aqua regia solution for 2 to 10 sec depending on the intensity of the contrast required and the surface is not subsequently washed. The results obtained with a coarse grained cast structure are shown in Fig. 2. Subgrain boundaries in a single crystal and concentration gradients within the boundaries are developed by the same treatment with the results shown in Fig. 3. Obviously, any conclusions regarding structure-dependent properties will be modified by the pronounced heterogeneity, which is not clearly evident when more conventional methods are used. Interesting structural details are also revealed by treatment for 4 hr at 850°C in unpurified tank argon. Fig. 4 shows a pattern characteristic of orientation-dependent oxidation.

Jan 1, 1956

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith's graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970

By A. K. Sinha

The annual production and productivity of underground coal mines in recent years declined from 334 Mt (368 million st) and 14.5 t (16 st) per man per shift in 1969 to approximately 254 Mt (280 million st) and less than 8 t (9 st) per man per shift in 1977. Productivity is still hovering at about 7.25 t (8 st) per man per shift. According to US Bureau of Mines, the estimated US coal reserve is about 396 Gt (437 billion st), 68.65% of which is obtainable by underground mining methods. Approximately 153 Gt (169 billion st), or about 85.2% of the high Btu premium coking coal of the eastern US, would need to be extracted by underground mining methods. It is thus apparent that under- ground mining will continue to play a major role in total US coal production, which is expected to rapidly increase to about 1.1 Gt (1.2 billion st) by 1985, with about 606 Mt (668 million st) being contributed by underground mines. Production Potential of Continuous Mining The production potential of a continuous mining section depends primarily on the producing ability of the miner, transporting ability of the face haulage, and the matching of the two systems. The producing ability of the continuous miner depends on its actual cutting ability and the time available for cutting coal. The performance of 10 continuous miners operating in coal seams of various thicknesses were monitored in Pennsylvania and West Virginia, using continuous electrical power analyzers and time studies. The recordings on current and power strip charts yielded an accurate analysis of the cutting, trimming, and idle times of the machines on a full shift basis. Continuous miners of various models and sizes from 112-298 kW (150-400 hp) were monitored. Based on actual cutting time, the average cutting ability of the machines, as shown in [Fig. 1], ranged from

Jan 1, 1983

By Goro Shimaoka, Kichizo Niwa

IN the past, the crystalline states of graphite in cast iron have been studied by many investigators. Recently several authors 1-4 have published interesting information on the crystal texture of the individual graphite grain, especially spherulites in nodular cast iron. In regard to the crystal structure of graphite, Lipson and Stokes0 howed by powder X-ray analysis that most of the crystals contain about 14 pct rhombohedra1 structure (ß-form) which differs from the hexagonal structure (a-form) in the sequence of layer stacking. Hoerni6 onfirmed the existence of the ß-form in a single crystal with electron diffraction by Kossel-Moellenstedt's method. Furthermore, Hoerni and Weigle7 found extra reflections in electron diffraction patterns, which are given by a unit cell twice as large as the usual one in the basal plane. Recently, Lukeshs observed graphite twinning and satellite reflections in his X-ray work and considered them as evidence for the existence of an orthorhombic superstructure. Owen and Street" and Matuyama" studied the structures of graphite crystals in several types of cast iron, using the X-ray powder method, and they showed that the graphite crystal contains a certain amount of the ß-form, an amount which varies with the sources of the cast iron used. The present study was made in order to secure structural information on graphitization in cast iron. Electron diffraction studies on the structure of single graphite flakes segregated from molten carbon or silicon-rich iron at 1200" to 1500°C are reported. Experimental Honkeiko pig iron (4.05 pct C, 1.59 pct Si, and 0.65 pct Mn) was used as the solvent of carbon or silicon. The pig iron was melted in an open furnace and a small quantity of metallic silicon was added to the melt at 1300°C. The melt was heated to 150O°C, and then retort black carbon or metallic silicon was added little by little. The components added to the bath contained approximately 5.0 pct C and 2.0 pct Si in the carbon-rich material, and 3.8 pct C and 5.4 pct Si in the silicon-rich iron. These two types were held at 1500°C and then cooled without graphitizing by cutting the heat sup-

Jan 1, 1958

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

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

Jan 1, 1963

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth's crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO3), brucite (Mg[OH]2), dolomite (CaMg[C03]2), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe]2Si04), talc (H2Mg3[Si03]4), and serpentine (H4Mg3Si2O9). These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia-containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with seawater or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombohedral carbonates which includes calcite (CaC03), siderite (FeCO3), and rhodochrosite (MnCO3) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgCO3-CaCO3 series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO.. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or amorphous (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellow, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1983

By N. J. Grant, D. S. Bloom

N recent reports, Sully' and Beck and coworkers' I have advanced hypotheses concerning the formation of the phase. Both of these hypotheses are based on Pauling's theories of the electronic configuration of the elements of the first transition group. Sully considered that the number of electrons which can be absorbed in filling electron "holes" is the factor which determines whether or not the structure can form. Beck suggested that the presence of a certain concentration of electron "holes" is the controlling value. It can be shown that a similar criterion can be developed without making reference to Pauling's theories. Table I shows the elements of the first transition group and the incidence of the a structure in the binary systems of these elements according to the data presently available. Also appended is the number of electrons considered to exist in the 3d-4s levels of these elements. If the atomic percentages for the phase are listed as shown in Table 11, and if the number of electrons in the 3d-4s levels per atom is calculated for the a boundary values, the results are as shown in the last column. It can be seen that the numerical values are all in the vicinity of 7 electrons per atom. This is true also for the ternary Cr-Mo-Ni IT phase, which occurs in a system in which none of the binary compositions are known to develop the phase. In the Fe-Mo binary, the high temperature a phase, which occurs at a composition of 50 atomic pct of each element, also yields a ,;1 e of 7 electrons per atom. From inspection of Tables I and 11, it develops that any series of sequential numbers which is assigned to the elements under consideration will result in the numbers pertaining to a compositions grouping themselves around one specific number. It does not follow, however, that this random number necessarily has physical significance. Such a point has already been discussed by Hume-Rothery." One interesting point develops from this study, however, and that is the position of manganese with reference to the other elements and to the phase. In the system used here, the formation of phase is associated approximately with the value of 7 electrons per atom, which is also the number of electrons per atom that manganese has. Manganese, it will be recalled, exists in three different crystal forms, none of which are the usual, simpler metallic forms; on the other hand, elements just to the left of manganese (in Table I) generally have lower coordination-number structures (body-centered cubic) than do elements to the right of manganese (face-centered cubic). The contribution to a complex crystal structure by the interalloying of elements from opposite sides of manganese is significant in that the a phase is formed in binary systems including one element from each side of manganese, with manganese capable of participating with both sides. It is indeed an interesting coincidence that manganese, with 7 electrons per atom, solidifies in complex crystal forms, and that when alloys of the transition elements are made which have seven 3d-4s electrons per atom, they, too, tend to assume a complex crystal form. From the above, it might be deduced that the study of the a phase might be advanced by a critical examination of the element manganese and how its structure is affected by small additions of elements which change the 3d-4s electrons per atom number. The role of atom size would also be of interest in formation. References ' A. H. Sully: The Sigma Phase in Binary Alloys of the Transition Elements. Journal Inst. Metals (1951) 80, Part 4, p. 173. 2 S. Rideout, W. D. Manly, E. L. Kamen, B. S. Lement, and P. A. Beck: Intermediate Phases in Ternary Alloy Systems of Transition Elements. Trans. AIME (1951) 191, p. 872; Journal of Metals (October 1951). "W. Hume-Rothery, H. M. Irving, and R. J. P. Williams: The Valencies of the Transition Elements in the Metallic State. Proc. Royal Soc. (September 1951) 208A. p. 431.

Jan 1, 1954

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By Earnshaw Cook, J. A. Fellows, Howard S. Avery

Heat-resistant alloys of the higher nickel and chromium ranges have been empirically developed through the practical experience of the past two decades to a position of significant industrial importance. Few quantitative metallurgical data have been published, however, that could be related directly to engineering specifications and design. Inadequate information led to the inauguration, in 1934, of a research directed toward a better understanding of the properties and performance of these steels at temperatures between 1400° and 2000°F. Investigation was concentrated upon the 26 per cent Cr:I2 per cent Ni type, which owes its extensive application to an excellent combination of economy, strength and surface stability at elevated temperatures. The requirements of the oil-refining industry have been prominent in influencing the scope and evolution of the program. Creep strength at the maximum allowable deformation ranges has been employed to evaluate the merits of these alloys. Permissible elongation rates vary from 1.0 per cent in one million hours for turbine blades to I .o per cent in ten thousand hours for tube supports and heating-furnace equipment. Throughout this paper, the limiting creep stress (L.C.S.) for a given temperature has been defined as the stress that will produce a uniform elongation rate (stage 11) of one per cent in ten thousand hours as extrapolated from rates per hour for tests of less than two thousand hours duration. Certain current specifications require a minimum L.C.S. of 1600 lb. per sq. in. at I800°F., of 3600 lb. per sq. in. at 1400°F., and include a tensile acceptance test at room temperature, after aging for 24 hr. at 1400°F., as a measure of embrittlement in service. An elongation of 4 per cent is considered satisfactory for general use, while a minimum of 9 per cent is prescribed on occasion. Many differences of opinion concerning the properties and performance of these alloys appear to result from their sensitivity to unappreciated variations of chemical analyses which, for example, may change their L.C.S. from 3500 to 350 lb. per sq. in. at 1800°F. Within broad chemical limits, it is possible to balance the six or more important elements present to attain desirable properties with a number of different combinations. One method for adjusting the composition has been described under the sponsorship of the Alloy Casting Institute,' in which, by maintaining a substantially austenitic* alloy, optimum creep strength and minimum tendency to embrittle after aging are expected. Unless, however, the limits are undesirably close, it has not been possible to ensure a moderate range of strength and of ductility by any chemical specification alone. There is a definite need

Jan 1, 1942

By J. A. Fellows, Earnshaw Cook, Howard S. Avery

Heat-resistant alloys of the higher nickel and chromium ranges have been empirically developed through the practical experience of the past two decades to a position of significant industrial importance. Few quantitative metallurgical data have been published, however, that could be related directly to engineering specifications and design. Inadequate information led to the inauguration, in 1934, of a research directed toward a better understanding of the properties and performance of these steels at temperatures between 1400° and 2000°F. Investigation was concentrated upon the 26 per cent Cr:I2 per cent Ni type, which owes its extensive application to an excellent combination of economy, strength and surface stability at elevated temperatures. The requirements of the oil-refining industry have been prominent in influencing the scope and evolution of the program. Creep strength at the maximum allowable deformation ranges has been employed to evaluate the merits of these alloys. Permissible elongation rates vary from 1.0 per cent in one million hours for turbine blades to I .o per cent in ten thousand hours for tube supports and heating-furnace equipment. Throughout this paper, the limiting creep stress (L.C.S.) for a given temperature has been defined as the stress that will produce a uniform elongation rate (stage 11) of one per cent in ten thousand hours as extrapolated from rates per hour for tests of less than two thousand hours duration. Certain current specifications require a minimum L.C.S. of 1600 lb. per sq. in. at I800°F., of 3600 lb. per sq. in. at 1400°F., and include a tensile acceptance test at room temperature, after aging for 24 hr. at 1400°F., as a measure of embrittlement in service. An elongation of 4 per cent is considered satisfactory for general use, while a minimum of 9 per cent is prescribed on occasion. Many differences of opinion concerning the properties and performance of these alloys appear to result from their sensitivity to unappreciated variations of chemical analyses which, for example, may change their L.C.S. from 3500 to 350 lb. per sq. in. at 1800°F. Within broad chemical limits, it is possible to balance the six or more important elements present to attain desirable properties with a number of different combinations. One method for adjusting the composition has been described under the sponsorship of the Alloy Casting Institute,' in which, by maintaining a substantially austenitic* alloy, optimum creep strength and minimum tendency to embrittle after aging are expected. Unless, however, the limits are undesirably close, it has not been possible to ensure a moderate range of strength and of ductility by any chemical specification alone. There is a definite need

Jan 1, 1942

By Persifor Frazer

I DESIRE to say that, owing to the number of papers which have been more or less crowded at this session of the Institute, and the fact that, as one of the Local Committee, I have the distinguished honor to feel somewhat like one of the hosts, I should not tax the patience of members at this late hour, but would have my paper read by title were it in any way possible to do this. But the task I have set myself this evening is to present to the eyes of the members of the Institute certain objects which have occupied more or less of my time during the last eighteen months or two years. The objects I allude to are some of the igneous rocks of this country, which, until quite recently, have been less understood than any others. It will be well known to some of the members that some of the cooled lavas of a previous age of our planet, when not directly coarsely crystalline and granular, were considered and spoken of as " natural glasses," or perfectly uncrystalline, vitreous, or hyaline masses of matter. Among the first results of the use of the microscope was the dispersion of this fallacy. Sir David Brewster, Mr. H. C. Sorby, and William Nichol (the discoverer of the celebrated calcite prism, which bears his name), had, with greater or less success, examined sections of various rocks and minerals, both by transmitted and reflected light, and also in the form of powder. But, until the genius of Vogelsang undertook the subject, these investigations had no permanent value, nor did they constitute an independent line of mineralogical and geological research. Since the close of his labors, by Vogelgang's premature and much-lamented death, the subject has been made one of renewed interest by his brother-in-law, Ferdinand Zirkel, as well as by Rosenbusch, Tschermak, and many others abroad, and at home by the commencement of a systematic study of the traps of Connecticut by Messrs. E. D. Dana and G. W. Hawes, of New Haven, and by the splendid set of described sections of the traps of the West which have been furnished by Zirkel to illustrate Clarence King's report. I had the honor of presenting a large number of thin sections of our traps at the Washington meeting, for the inspection of the mem¬bers, with the aid of a table microscope belonging to the Smithsonian Institution. Here I propose to project these sections upon the

Jan 1, 1877

By A. V. Deforest, C. W. Macgregor, A. R. Anderson

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942

By A. V. Deforest, A. R. Anderson, C. W. MacGregor

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942